WO2020230714A1 - Resin composition and ultraviolet light-emitting device - Google Patents
Resin composition and ultraviolet light-emitting device Download PDFInfo
- Publication number
- WO2020230714A1 WO2020230714A1 PCT/JP2020/018653 JP2020018653W WO2020230714A1 WO 2020230714 A1 WO2020230714 A1 WO 2020230714A1 JP 2020018653 W JP2020018653 W JP 2020018653W WO 2020230714 A1 WO2020230714 A1 WO 2020230714A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- fluororesin
- less
- structural unit
- molar ratio
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 82
- 239000000470 constituent Substances 0.000 claims abstract description 62
- 239000011256 inorganic filler Substances 0.000 claims abstract description 58
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 58
- 238000007789 sealing Methods 0.000 claims abstract description 23
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 9
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 17
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 description 30
- 239000011347 resin Substances 0.000 description 28
- 229920005989 resin Polymers 0.000 description 28
- 239000002904 solvent Substances 0.000 description 24
- 238000002844 melting Methods 0.000 description 21
- 230000008018 melting Effects 0.000 description 21
- 239000000945 filler Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000010354 integration Effects 0.000 description 5
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229940090181 propyl acetate Drugs 0.000 description 5
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 5
- 229920003249 vinylidene fluoride hexafluoropropylene elastomer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910002704 AlGaN Inorganic materials 0.000 description 4
- 238000004438 BET method Methods 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical group CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920009638 Tetrafluoroethylene-Hexafluoropropylene-Vinylidenefluoride Copolymer Polymers 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003759 ester based solvent Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000005453 ketone based solvent Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- -1 perfluoroalkyl vinyl ether Chemical compound 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229910015363 Au—Sn Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 235000014443 Pyrus communis Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- GHDBATCSDZIYOS-UHFFFAOYSA-N 1,1,2,3,3,4,4-heptafluoro-4-(1,2,2-trifluoroethenoxy)but-1-ene Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)=C(F)F GHDBATCSDZIYOS-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
Definitions
- the present invention relates to a resin composition and an ultraviolet light emitting device.
- Non-Patent Document 1 a perfluoro (4-vinyloxy-1-butene) (BVE) polymer having a CF 3 terminal is used for encapsulating a deep ultraviolet AlGaN LED because it has excellent durability against deep ultraviolet rays. It is stated that it can be done.
- Patent Document 1 discloses an ultraviolet light emitting device in which an ultraviolet light emitting element is sealed with an amorphous fluororesin.
- Patent Document 2 discloses that a fluoropolymer (THV) containing at least tetrafluoroethylene (TFE), hexafluoropropylene (HFP) and vinylidene fluoride (VdF) is used for encapsulating an LED element.
- TFE tetrafluoroethylene
- HFP hexafluoropropylene
- VdF vinylidene fluoride
- Patent Document 3 describes that a resin composition containing a fluororesin and a heat conductive material having a thermal conductivity of 1.5 W / mK or more is suitably used for a wavelength conversion member, a sealing member, and the like. ing.
- a composition containing a fluororesin having high durability against ultraviolet rays is used.
- Such a fluororesin-containing composition is expected to improve not only the durability against ultraviolet rays but also the heat resistance of the ultraviolet light emitting element against heat generation and the adhesion of the ultraviolet light emitting device to the base material and the like.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition having excellent heat resistance and adhesion. Another object of the present invention is to provide an ultraviolet light emitting device having excellent heat resistance and adhesion of a sealing portion.
- the resin composition of the present invention and the ultraviolet light emitting device capable of solving the above problems have the following configurations.
- the fluororesin contains a constituent unit A derived from tetrafluoroethylene, a constituent unit B derived from hexafluoropropylene, and a constituent unit C derived from vinylidene fluoride.
- the molar ratio (A) of the structural unit A to the total of the structural unit A, the structural unit B, and the structural unit C is 0.25 or more.
- a resin composition, wherein the molar ratio (C) of the structural unit C to the total of the structural unit A, the structural unit B, and the structural unit C is 0.60 or less.
- the molar ratio (B) of the structural unit B to the total of the structural unit A, the structural unit B, and the structural unit C is 0.05 or more and 0.50 or less [1] to [3].
- FIG. 1 is a cross-sectional view schematically showing an example of an ultraviolet light emitting element.
- FIG. 2 is a cross-sectional view schematically showing an example of an ultraviolet light emitting device before the ultraviolet light emitting element is sealed by the solidified resin composition of the present invention.
- FIG. 3 is a cross-sectional view schematically showing an example of an ultraviolet light emitting device in which an ultraviolet light emitting element is sealed by a solidified product of the resin composition of the present invention.
- FIG. 4 is a cross-sectional view schematically showing another example of an ultraviolet light emitting device in which an ultraviolet light emitting element is sealed by a solidified product of the resin composition of the present invention.
- the resin composition of the present invention contains a fluorine resin and an inorganic filler, and the fluorine resin contains a constitutional unit A derived from tetrafluoroethylene, a constitutional unit B derived from hexafluoropropylene, and a constitutional unit C derived from vinylidene fluoride.
- the molar ratio (A) of the constituent unit A to the total of the constituent unit A, the constituent unit B, and the constituent unit C is 0.25 or more, and the constituent unit with respect to the total of the constituent unit A, the constituent unit B, and the constituent unit C. It is characterized in that the molar ratio (C) of C is 0.60 or less.
- a structural unit A derived from tetrafluoroethylene, a structural unit B derived from hexafluoropropylene, and a structural unit C derived from vinylidene fluoride are included, and a structural unit with respect to the total of the structural unit A, the structural unit B, and the structural unit C.
- the molar ratio (A) of the constituent unit A to the total of the constituent unit A, the constituent unit B, and the constituent unit C is 0.25 or more. This tends to improve the adhesion. Therefore, the lower limit of the molar ratio (A) of the structural unit A is more preferably 0.28 or more, still more preferably 0.30 or more. On the other hand, the upper limit of the molar ratio (A) of the constituent unit A is preferably 0.75 or less, more preferably 0.60 or less, still more preferably 0.50 or less from the viewpoint of transparency.
- the molar ratio (C) of the constituent unit C to the total of the constituent unit A, the constituent unit B, and the constituent unit C is 0.60 or less. This tends to improve the adhesion. Therefore, the upper limit of the molar ratio (C) of the structural unit C is preferably 0.58 or less, more preferably 0.56 or less. On the other hand, the lower limit of the molar ratio (C) of the structural unit C is preferably 0.20 or more. As a result, the solubility in an organic solvent is improved, so that the number of times the resin composition is applied can be reduced when sealing the ultraviolet light emitting element. Therefore, the lower limit of the molar ratio (C) of the structural unit C is more preferably 0.30 or more, still more preferably 0.40 or more, and even more preferably 0.50 or more.
- the molar ratio (B) of the structural unit B to the total of the structural unit A, the structural unit B, and the structural unit C is preferably 0.05 or more and 0.50 or less.
- the lower limit of the molar ratio (B) of the structural unit B is more preferably 0.07 or more, still more preferably 0.09 or more, from the viewpoint of solubility.
- the upper limit of the molar ratio (B) of the constituent unit B is more preferably 0.40 or less, still more preferably 0.30 or less, still more preferably 0.20 or less from the viewpoint of heat resistance.
- the ratio of the molar ratio (C) to the molar ratio (A) is preferably 0.20 or more and 3.50 or less.
- the lower limit of the molar ratio (C) / molar ratio (A) is more preferably 0.50 or more, still more preferably 1.00 or more, even more preferably 1.30 or more, particularly preferably 1.45 or more, most preferably. Is 1.50 or more.
- the upper limit of the molar ratio (C) / molar ratio (A) is more preferably 3.00 or less, still more preferably 2.50 or less, and even more preferably 2.00 or less.
- the ratio of the molar ratio (B) to the molar ratio (A) is preferably 0.10 or more and 0.80 or less.
- the lower limit of the molar ratio (B) / molar ratio (A) is more preferably 0.20 or more, still more preferably 0.24 or more, and even more preferably 0.28 or more.
- the upper limit of the molar ratio (B) / molar ratio (A) is more preferably 0.60 or less, still more preferably 0.50 or less, and even more preferably 0.40 or less.
- the molar ratio of each constituent unit of the fluororesin can be obtained by the NMR measurement described in Examples described later.
- NMR measurement described in Examples described later.
- calculating the molar ratio for example, Eric B. Twum et al., “Multidimensional 19F NMR Analyses of Terpolymers from Vinylidene Fluoride (VDF) -Hexafluoropropylene (HFP) -Tetrafluoroethylene (TFE)”, Macromolecules, Vol. No., p.3563-3576 can be referred to.
- the fluororesin of the present invention contains a constituent unit A derived from tetrafluoroethylene, a constituent unit B derived from hexafluoropropylene, and a constituent unit C derived from vinylidene fluoride, but the constituent unit A, the constituent unit B, and the constituent unit It may include other structural units other than C. Examples of other structural units include ethylene-derived structural units, perfluoroalkyl vinyl ether-derived structural units, and chlorotrifluoroethylene-derived structural units.
- the refractive index of the fluororesin of the present invention is preferably more than 1.34, more preferably 1.35 or more, still more preferably 1.36 or more.
- the difference in the refractive index between the ultraviolet light emitting element and the sealing portion which will be described later, can be reduced, the total reflection at the interface between the ultraviolet emitting element and the sealing portion can be reduced, and the light extraction efficiency can be improved. it can.
- the light extraction efficiency is the efficiency at which the light generated by the ultraviolet light emitting element is extracted to the outside of the ultraviolet light emitting element.
- the upper limit of the refractive index of the fluororesin of the present invention is, for example, 1.45 or less, and may be 1.40 or less.
- the refractive index may be a value described in a catalog value or a general physical property table, or may be measured by a method described in Examples described later using a commercially available Abbe refractive index meter or ellipsometer. You can also.
- the refractive index described in the present application is a value at the wavelength of the commonly used sodium D line (589 nm).
- the total molar ratio of the constituent unit A, the constituent unit B, and the constituent unit C to all the constituent units of the fluororesin of the present invention is preferably 0.70 or more, more preferably 0.80 or more, still more preferably 0.90 or more. , Especially preferably 0.95 or more, and most preferably 1. That is, it is most preferable that all the constituent units of the fluororesin of the present invention are composed of the constituent unit A, the constituent unit B, and the constituent unit C. As a result, the adhesion tends to be improved.
- the weight average molecular weight of the fluororesin of the present invention is preferably 50,000 or more and 1,000,000 or less. By setting the weight average molecular weight to 50,000 or more, the viscosity at the time of melting can be increased, so that the shape change of the sealing resin at the time of lighting the LED can be suppressed.
- the lower limit of the weight average molecular weight of the fluororesin of the present invention is more preferably 100,000 or more, still more preferably 200,000 or more, still more preferably 250,000 or more, and particularly preferably 300,000 or more.
- the solubility is improved by setting the weight average molecular weight of the fluororesin of the present invention to 1,000,000 or less.
- the upper limit of the weight average molecular weight of the fluororesin of the present invention is more preferably 800,000 or less, still more preferably 500,000 or less, even more preferably 450,000 or less, and particularly preferably 400,000 or less.
- the weight average molecular weight is a standard polystyrene conversion value.
- the fluororesin of the present invention may be either a random copolymer or a block copolymer, but is preferably a random copolymer.
- the fluororesin of the present invention preferably has a melting point of 90 ° C. or higher and 278 ° C. or lower.
- the lower limit of the melting point of the fluororesin of the present invention is more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and even more preferably 115 ° C. or higher.
- the melting point is 278 ° C. or lower, the fluororesin of the present invention is easily melted by heating, so that the ultraviolet light emitting element can be easily sealed by heating and melting.
- the melting point of Au-Sn (20% by mass), which is a general solder material is 278 ° C.
- the melting point of the resin is 278 ° C. or less, so that it is easy to prevent the bumps described later from melting due to heating. can do.
- the upper limit of the melting point of the fluororesin of the present invention is more preferably 200 ° C. or lower, still more preferably 170 ° C. or lower, still more preferably 150 ° C. or lower, and particularly preferably 130 ° C. or lower.
- a catalog value may be used, or for example, using a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Co., Ltd.), the temperature rise rate is 10 ° C./min and the temperature is -50 ° C. to 200 ° C. It can be obtained by changing the temperature to the above temperature and measuring the melting peak temperature (Tm) from the melting curve obtained thereby.
- DSC differential scanning calorimeter
- the inorganic filler examples include metal fluoride, metal oxide, metal phosphate, metal carbonate, metal sulfonate, metal nitrate, metal nitride, boron nitride and the like.
- the inorganic filler may be used alone or in combination of two or more.
- the inorganic filler is preferably a metal fluoride from the viewpoint of preventing thermal decomposition and transparency.
- the metal fluoride include calcium fluoride, barium fluoride, strontium fluoride, lithium fluoride, sodium fluoride, magnesium fluoride, glacial stone and the like. Of these, magnesium fluoride is preferable. These may be used alone or in combination of two or more.
- the inorganic filler may be a polycrystalline body or a single crystal body, but from the viewpoint of facilitating the improvement of the light transmittance of the resin molded body by reducing the scattering of light at the grain boundaries, or the resin molding.
- the grain boundaries contained in the particles are small, and it is particularly preferable to use a single crystal. Whether or not the inorganic filler is a single crystal can be determined by, for example, confirming the electron diffraction pattern with an electron microscope.
- the particle size of the inorganic filler is preferably 300 ⁇ m or less. When the inorganic filler is 300 ⁇ m or less, discoloration due to an increase in temperature of the resin composition can be reduced.
- the particle size of the inorganic filler is more preferably 200 ⁇ m or less, still more preferably 100 ⁇ m or less, even more preferably 50 ⁇ m or less, particularly preferably 30 ⁇ m or less, and particularly preferably 20 ⁇ m or less.
- the particle size of the inorganic filler is preferably 0.5 ⁇ m or more. By setting the particle size of the inorganic filler to 0.5 ⁇ m or more, it is possible to suppress light scattering between the resin and the filler, and the transparency of the resin is excellent.
- the lower limit of the particle size of the inorganic filler is more preferably 1 ⁇ m or more, still more preferably 5 ⁇ m or more.
- the particle size of this inorganic filler is a particle size D 50 having a volume accumulation frequency of 50% by a laser diffraction method.
- the difference in refractive index between the fluororesin of the present invention and the inorganic filler is preferably 0.05 or less. By reducing the difference in refractive index in this way, it is possible to suppress light scattering on the surface of the inorganic filler (the interface between the surface of the inorganic filler and the fluororesin in the composition), thereby improving the light extraction efficiency. be able to.
- the difference in refractive index between the fluororesin of the present invention and the inorganic filler is more preferably 0.04 or less, still more preferably 0.03 or less.
- the lower limit of the difference in refractive index between the fluororesin of the present invention and the inorganic filler is not particularly limited, but may be, for example, 0.001 or more.
- the refractive index of the inorganic filler of the present invention may be a value described in a catalog value or a general physical property table, or may be measured by a method described in Examples described later such as an Abbe refractive index meter and an ellipsometer. Can be done.
- the specific surface area (surface area per 1 g) of the inorganic filler is preferably 30 m 2 / g or less. By reducing the specific surface area in this way, coloring of the resin composition can be suppressed, and a resin composition having particularly excellent permeability in the ultraviolet region can be obtained.
- the specific surface area is more preferably 20 m 2 / g or less, further preferably 10 m 2 / g or less, particularly preferably 5 m 2 / g or less, particularly preferably 3 m 2 / g or less, and 0. it may also be .1m 2 / g or more, may be 0.5 m 2 / g or more.
- a method for measuring the specific surface area using the BET method can be used for example.
- the amount of the inorganic filler with respect to a total of 100 parts by mass of the fluororesin and the inorganic filler of the present invention is preferably 1 part by mass or more and 60 parts by mass or less.
- the lower limit of the amount of the inorganic filler is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more.
- the upper limit of the amount of the inorganic filler is more preferably 50 parts by mass or less, still more preferably 45 parts by mass or less.
- the amount of the fluororesin of the present invention with respect to a total of 100 parts by mass of the fluororesin of the present invention and the inorganic filler is preferably 40 parts by mass or more and 99 parts by mass or less.
- the amount of the fluororesin of the present invention is 40 parts by mass or more, the adhesion of the fluororesin of the present invention can be easily exhibited. Therefore, the lower limit of the amount of the fluororesin of the present invention is more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more.
- the upper limit of the amount of the fluororesin of the present invention is more preferably 90 parts by mass or less, still more preferably 85 parts by mass or less.
- the resin composition can be produced by mixing the fluororesin of the present invention and an inorganic filler. These mixings may be, for example, melt kneading, or the fluororesin of the present invention may be mixed with an inorganic filler in a molten state, or the fluororesin of the present invention may be dissolved or the fluororesin may be dissolved. It may be mixed with an inorganic filler in the presence of a dispersing solvent.
- the resin composition may be a solid material or a fluid material. In the case of a fluid, it may contain a solvent.
- the solvent examples include organic solvents.
- an organic solvent an ester solvent such as ethyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl propionate, glycol ester obtained by adding an acetate group to glycol ether; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
- Ketone-based solvent such as diethyl ether, dipropyl ether, butyl ether, glycol ether, terrorahydrofuran; amide-based solvent such as N, N-dimethylformamide, N, N-dibutylformamide, N, N-dimethylacetamide Solvents; lactam solvents such as N-methyl-2-pyrrolidone; and the like.
- ester-based solvents, ketone-based solvents, and ether-based solvents are preferable, and ester-based solvents are more preferable.
- These organic solvents may be used alone or in combination of two or more.
- the amount of the solvent with respect to 100 parts by mass of the fluororesin of the present invention is preferably 100 parts by mass or more and 5000 parts by mass or less.
- the amount is 100 parts by mass or more, the fluororesin of the present invention can be easily dissolved or dispersed.
- the amount of the solvent is more preferably 200 parts by mass or more, further preferably 400 parts by mass or more, and even more preferably 600 parts by mass or more.
- the amount is 5000 parts by mass or less, the number of times of coating for sealing the ultraviolet light emitting device can be reduced.
- the amount of the solvent is more preferably 2000 parts by mass or less, further preferably 1200 parts by mass or less, and even more preferably 1000 parts by mass or less.
- the solvent may be reduced by volatilization or the like, if necessary.
- the amount of the solvent after reduction with respect to 100 parts by mass of the fluororesin of the present invention is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 20 parts by mass. It is as follows.
- the resin composition may also contain a fluororesin, an additive, etc. other than the fluororesin of the present invention.
- fluororesins examples include crystalline fluororesins, and specifically, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and chlorotri.
- PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- chlorotri examples thereof include a fluoroethylene polymer (PCTFE), a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) that does not satisfy the predetermined ratio of the constituent unit A and the constituent unit C of the present invention.
- PCTFE fluoroethylene polymer
- TSV tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copo
- the amount of the other fluororesin with respect to 100 parts by mass of the fluororesin of the present invention is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, and particularly preferably 1 part by mass or less. Is 0 parts by mass. That is, the fluororesin contained in the resin composition of the present invention is most preferably made of the fluororesin of the present invention. As a result, the difference in refractive index between the resins can be reduced and the light extraction efficiency can be improved.
- the total content of the total fluororesin (total of the fluororesin of the present invention and other fluororesins) and the inorganic filler with respect to the total mass of the resin composition (solid content) is preferably 90% by mass or more, preferably 95% by mass or more. Is more preferable, 97% by mass or more is even more preferable, and 99% by mass or more is particularly preferable. This makes it easier for the fluororesin to improve the adhesion and the inorganic filler to improve the heat resistance.
- the resin composition of the present invention can be made into a solidified product (resin molded product) by, for example, lowering the temperature below the melting point or volatilizing the solvent. Since the resin composition of the present invention has excellent durability against ultraviolet rays, and also has excellent adhesion and heat resistance, it can be suitably used for sealing an ultraviolet light emitting element.
- the heat resistance of the resin composition can be evaluated by performing thermal weight measurement (TG measurement) and measuring the temperature (10% mass change temperature) when the mass of the fluororesin itself is reduced by 10 mass%. it can.
- the 10% mass change temperature is preferably 400 ° C. or higher because the resin composition has excellent heat resistance. In the examples described later, the 10% mass change temperature was measured under the following conditions. Sampling is preferably performed at least twice before the temperature rises by 1 ° C. as in the following conditions. Sampling is performed at predetermined intervals (seconds), and the temperature at the first sampling after the time when the mass of the fluororesin is reduced by 10% by mass is defined as the 10% mass change temperature.
- the present invention also includes an ultraviolet light emitting device including an ultraviolet light emitting element in which the ultraviolet light emitting element is sealed with a solidified product of the above resin composition.
- an ultraviolet light emitting device including an ultraviolet light emitting element in which the ultraviolet light emitting element is sealed with a solidified product of the above resin composition.
- FIG. 1 is a cross-sectional view schematically showing an example of an ultraviolet light emitting element.
- FIG. 2 is a cross-sectional view schematically showing an example of an ultraviolet light emitting device (hereinafter, may be referred to as an ultraviolet light emitting element mounting package) before being sealed by the solidified product of the resin composition of the present invention.
- Is a cross-sectional view schematically showing an example of an ultraviolet light emitting device sealed with a solidified product of the resin composition of the present invention
- FIG. 4 is an ultraviolet ray sealed with a solidified product of the resin composition of the present invention. It is sectional drawing which shows another example of a light emitting device schematically.
- the ultraviolet light emitting element 2 of FIG. 1 is a flip-chip type element, has a p electrode 10 on the anode side on a part of the lower side surface, and a p layer 12 is formed on the p electrode 10. Further, another part of the lower side surface of the ultraviolet light emitting element 2 is provided with an n electrode 11 on the cathode side, and an n layer 14 is formed on the n electrode 11.
- the n-electrode 11 and the n-layer 14 are formed by shifting upward from the p-electrode 10 and the p-layer 12, and are active between the n-layer 14 existing above and the p-layer 12 existing below. Layer 13 is formed.
- the substrate 15 is further above the n-layer 14 that is further above.
- Examples of the n-layer 14 include a Si-containing AlGaN layer.
- Examples of the p-layer 12 include a Mg-containing GaN layer.
- the p-layer 12 may have a laminated structure with an electron block layer or the like, if necessary.
- Examples of the active layer 13 include an AlGaN layer.
- the bandgap energy can be controlled within the range of the bandgap energy (about 3.4 eV and about 6.2 eV) that GaN and AlN can take by adjusting, for example, the AlN mole fraction of the active layer 13. It is possible to obtain ultraviolet light emission having an emission wavelength of about 200 nm to about 365 nm.
- the emission peak wavelength of the ultraviolet light emitting element 2 is preferably 300 nm or less. Since the sterilization effect is easily exhibited when the emission peak wavelength is 300 nm or less, the ultraviolet light emitting element 2 can be used as a light emitting device for sterilization.
- the emission peak wavelength is more preferably 280 nm or less.
- Examples of the substrate 15 include a sapphire substrate and an aluminum nitride substrate.
- Examples of the material of the p electrode 10 include Ni / Au, and examples of the material of the n electrode 11 include Ti / Al / Ti / Au.
- the exposed surface between the p electrode 10 and the n electrode 11 may be covered with a protective insulating film such as SiO 2 in order to prevent a short circuit.
- the ultraviolet light emitting element mounting package 6 of FIG. 2 has a base material 4 made of ceramics such as aluminum nitride (AlN) and alumina (Al 2 O 3 ), and wiring (shown) is provided on the base material 4. , And metal bumps 5 such as Au and Au—Sn (20% by mass) alloy are formed on the wiring.
- the wiring (not shown) and the p-electrode 10 and n-electrode 11 of the ultraviolet light emitting element 2 are fixed so as to be electrically connected to each other via the bump 5.
- the ultraviolet light emitting element 2 of the ultraviolet light emitting element mounting package 6 shown in FIG. 2 is sealed with the solidified product 3a of the resin composition of the present invention, and silica glass and borosilicate glass are formed on the surface thereof.
- a condenser lens 7 made of acid glass or the like is formed. Although the light extraction efficiency can be improved by the condenser lens 7, the condenser lens 7 does not necessarily have to be provided.
- the ultraviolet light emitting device 1a of FIG. 4 is different from the ultraviolet light emitting device 1 of FIG. 3 in that the sealing member formed of the solidified product 3b of the resin composition of the present invention is raised upward to form a lens shape.
- the ultraviolet light emitting devices 1 and 1a of FIGS. 3 and 4 can be sealed by repeating the steps of applying and drying a solution of the resin composition of the present invention in an appropriate solvent one or more times.
- the solvent include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate and butyl acetate, cyclic ethers such as tetrahydrofuran, N-methyl-2-pyrrolidone and the like. Lactams are mentioned.
- the concentration of the resin composition in the coating liquid is, for example, 1% by mass or more. The higher the concentration, the less the number of coatings can be applied.
- the preferable concentration is 5% by mass or more, and more preferably 7% by mass or more.
- the concentration is, for example, 50% by mass or less.
- the lower the concentration the more the viscosity of the coating liquid can be prevented from being improved, and the processing accuracy can be improved.
- the preferable concentration is 40% by mass or less, and more preferably 30% by mass or less.
- the sealing of the ultraviolet light emitting devices 1 and 1a of FIGS. 3 and 4 can also be produced by heating the resin composition of the present invention to an appropriate temperature to melt it and pouring the melt onto the ultraviolet light emitting element 2.
- the heating temperature is equal to or higher than the melting point of the fluororesin, preferably melting point + 10 ° C. or higher, and more preferably melting point + 20 ° C. or higher.
- the upper limit of the heating temperature is, for example, 270 ° C, more preferably 200 ° C, and even more preferably 150 ° C.
- the resin composition of the present invention is molded into a sheet, and the sheet is laminated on the ultraviolet light emitting element mounting side of the ultraviolet light emitting element mounting package, and then. It can also be carried out by heating the sheet above its melting point to melt it and then cooling it (hereinafter, this sealing method may be referred to as a "melt sealing method").
- the heating temperature of the sheet is preferably 10 ° C. or higher higher than the melting point of the fluororesin, and more preferably 20 ° C. or higher higher than the melting point.
- the upper limit of the heating temperature is, for example, 278 ° C., more preferably 250 ° C., even more preferably 200 ° C., and particularly preferably 150 ° C. At the above heating temperature, deterioration of the ultraviolet light emitting element mounting package due to heat can be suppressed.
- the sheet may be heated in an oxygen-containing atmosphere such as the atmosphere, but it is preferably performed in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere.
- the fluororesin may be heated under atmospheric pressure, but it is also preferable to heat the fluororesin under reduced pressure such as in vacuum. When the fluororesin is heated under reduced pressure, the bubbles remaining in the resin after sealing are reduced and the transparency is improved.
- the sheet can be produced by producing pellets in which the fluororesin and the filler of the present invention are mixed and pressing, or if necessary, pressing while applying heat. Further, it can also be produced by mixing an inorganic filler with a molten fluororesin and extrusion molding.
- the pellet can be obtained by finely cutting a mixture of fluororesin and filler. For the mixture of fluororesin and filler, a method of mixing the filler with the fluororesin melted by heat, and a method of dissolving the fluororesin in a solvent to prepare a solution, then mixing the filler and drying the solvent.
- a method of precipitating the fluororesin with the filler involved is preferable.
- the light transmittance at a wavelength of 265 nm is preferably 8% or more, more preferably 30% or more, still more preferably 40% or more. Particularly preferably, it is 50% or more, and the transmittance of light at a wavelength of 350 nm is preferably 25% or more, more preferably 50% or more, still more preferably 60% or more, and particularly preferably 70% or more.
- the light transmittance at a wavelength of 500 nm is preferably 60% or more, more preferably 70% or more, still more preferably 75% or more, and particularly preferably 80% or more.
- the transparency of the sealing portion is improved, and the light extraction efficiency from the ultraviolet light emitting element can be improved.
- the light transmittance at a wavelength of 265 nm may be, for example, 80% or less, and the light transmittance at a wavelength of 350 nm may be, for example, 90% or less.
- the transmittance of light at a wavelength of 500 nm may be, for example, 95% or less.
- Measuring device JEOL ECZ-400 Sample: Approximately 60 mg / 0.8 ml ACT-d6 IS: 4-Chlorobenzodrifluoride 0.01 mL Measurement mode: 1 H, 19 F Relaxation time: 1 H 30 seconds, 19 F 20 seconds
- Number of units in building block B Calculated by dividing the integration ratio of CF 3 by 3 (CF 3 integration ratio / 3)
- Number of units in building block C Calculated by dividing the integration ratio of CH 2 by 2 (CH 2 integration ratio / 2)
- the number of units of the structural unit A than the total area ratio of CF 2, calculated by dividing the minus the CF 2 constituent units derived from C and CF 2 derived from structural units B in 4 ((CF 2 Total integration ratio - structure Number of units in unit C x 2-Number of units in configuration unit B x 2) / 4)
- Fluororesin containing no inorganic filler (resin compositions 1 and 2)
- a dam was formed on an Al substrate with a heat-resistant tape (thickness 0.19 mm, glass cloth tape) to prepare a plurality of regions having a length of 3.5 cm and a width of 4.0 cm.
- each of the fluororesins THV221AZ and DAI-EL G-501NK was added to propyl acetate to prepare a propyl acetate solution having a concentration of 9% by mass to obtain a resin composition 1 and a resin composition 2.
- the resin composition 1 and the resin composition 2 were placed in different regions by 400 ⁇ l each, and then heated and cooled at 200 ° C.
- the operation of mixing at 200 rpm for 3 minutes was performed twice to obtain a solution in which the filler was dispersed in the resin solution, that is, the resin composition 3 and the resin composition 4.
- the evaluation was carried out in the same manner as in (1) above, except that the resin composition 3 and the resin composition 4 were used.
- the solidified product of No. 3 showed excellent adhesion.
- the solidified product of No. 4 was inferior in adhesion.
- any of the following MgF 2 powders (1) to (3) was used as the inorganic filler.
- MgF 2 powder (2) having a specific surface area of 1.4 m 2 / g was obtained.
- Solvent Isopropyl alcohol (manufactured by Nacalai Tesque, Inc.) 100 g
- D 50 17 ⁇ m
- the particle size distribution of the inorganic filler is measured by obtaining an integrated distribution curve of the particle size of each prepared MgF 2 powder by a laser diffraction method under the following conditions, and obtaining the particle size D 50 , which is the particle size at a volume cumulative frequency of 50%. I went there.
- Measuring device SALD-2000J (manufactured by Shimadzu Corporation)
- Dispersion solvent Ion-exchanged water + Neutral detergent Dispersion method: Stirrer stirring + Ultrasonic irradiation 10 minutes Refractive index (MgF 2 ): 1.40-0.20i
- the inorganic filler was heat-treated at 150 ° C. for 30 minutes to prepare a measurement sample.
- the specific surface area of such a measurement sample was calculated by the BET method.
- Example 1 0.20 g of THV221AZ was placed on a quartz glass plate and melted by heating on a hot plate at 200 ° C. 0.08 g of MgF 2 powder (3) was added thereto, mixed using two spatula-shaped spatulas, and cooled to obtain a solidified resin composition.
- Example 2 THV221AZ was added to butyl acetate and dissolved so that the content of THV221AZ was 20% by mass. 8.0 g of the obtained mixed solution was weighed into a screw tube, and 0.29 g of MgF 2 powder (2) was added while stirring with a stirrer to obtain a uniform mixed solution. Next, 20 g of ethanol, which is a poor solvent, was added to precipitate a fluororesin containing a filler. The precipitated resin was taken out from the screw tube and dried at 80 ° C. for 5 hours to obtain a solidified resin composition.
- Example 3 A solidified resin composition was obtained in the same manner as in Example 2 except that the amount of the added MgF 2 powder (2) was changed to 0.65 g.
- Example 4 THV221AZ and MgF 2 powder (2) were kneaded under the following conditions to obtain a solidified resin composition.
- Kneading device Labplast Mill 3S150 (manufactured by Toyo Seiki Seisakusho Co., Ltd.)
- Mixer Roller mixer R60 Set temperature: 140 ° C
- Rotation speed 50 rpm Kneading time: 5 minutes
- Sample amount 100 g (THV221AZ: 71.2 g, MgF 2 powder: 28.8 g)
- Example 5 A solidified resin composition was obtained in the same manner as in Example 2 except that the amount of the added MgF 2 powder (2) was changed to 1.11 g.
- Example 6 A solidified resin composition was obtained in the same manner as in Example 2 except that the MgF 2 powder (1) was used and the amount of the added MgF 2 powder (1) was 1.11 g.
- Measuring device TG / DTA6200 (manufactured by SII Nanotechnology Co., Ltd.) Measurement atmosphere: Atmosphere Temperature range: 30 ° C to 500 ° C Temperature rise rate: 10 ° C / min Sampling interval: 4 seconds
- Example 7 160 g of butyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was weighed into a separable flask placed in a water bath, and the temperature of the water bath was raised to 85 ° C. with stirring. While stirring, 40 g of THV221AZ was gradually added and dissolved to prepare a resin solution. The obtained solution was heated at 120 ° C. for 3 hours, and the solid content concentration was determined from the residue and found to be 20.2% by mass.
- the resin solution having a concentration of 20.2% by mass prepared above was placed in a 15 g, 250 ml disposable cup, and 1.22 g of MgF 2 powder (2) was added thereto as a filler.
- the concentration of filler calculated the density of the resin 1.95 g / cm 3, the density of the MgF 2 powder as 3.15 g / cm 3, a 20% by volume.
- This solution is mixed with Awatori Rentaro ARV-310 at a rotation speed of 2000 rpm for 2 minutes three times to mix the solution and filler, and a magnetic stirrer is put therein and stirred to fill the filler.
- the sample was transferred to a petri dish made of PFA, defoamed and dried in a vacuum dryer at 200 ° C. for 3 hours.
- the sample was melted during drying and was agglomerated after drying.
- the obtained massive sample was cut again into a size of about 2 mm square using scissors to obtain pellets.
- the yield with respect to the total amount of the resin and the filler used was 100%.
- a 0.1 mm thick, 15 cm square polytetrafluoroethylene (PTFE) film is laminated on a 5 mm thick, 15 cm square SUS plate, and a 3 cm square through hole is provided in the center on the PTFE film.
- a 0.5 mm, 15 cm square SUS plate was laminated.
- the pellet was placed in the through hole of the 3 cm square. Further, a 0.1 mm thick, 15 cm square PTFE film and a 5 mm thick, 15 cm square SUS plate were laminated in this order to assemble a mold. Next, the temperature of the press was set to 200 ° C., and the upper and lower plates of the press were held in contact with the SUS plates above and below the die for 3 minutes without pressurization to melt the pellets. Then, the pressure was increased at 50 MPa for 2 minutes.
- Ultraviolet light emitting device 1a Ultraviolet light emitting device 2
- Ultraviolet light emitting element 3a 3b Solidified resin composition 4
- Base material 5 Bump 6
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Led Device Packages (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Provided are a resin composition that exhibits an excellent heat resistance and adhesiveness, and an ultraviolet light-emitting device that exhibits an excellent heat resistance and adhesiveness for the sealing part. A resin composition comprises a fluororesin and an inorganic filler, wherein the fluororesin contains a tetrafluoroethylene-derived constituent unit A, a hexafluoropropylene-derived constituent unit B, and a vinylidene fluoride-derived constituent unit C. The resin composition is characterized in that the molar ratio (A) of the constituent unit A to the sum of the constituent unit A, the constituent unit B, and the constituent unit C is at least 0.25, and the molar ratio (C) of the constituent unit C to the sum of the constituent unit A, the constituent unit B, and the constituent unit C is not more than 0.60.
Description
本発明は、樹脂組成物、および紫外線発光装置に関する。
The present invention relates to a resin composition and an ultraviolet light emitting device.
これまでにＬＥＤ（Ｌｉｇｈｔ Ｅｍｉｔｔｉｎｇ Ｄｉｏｄｅ）等の発光素子を備えた発光装置は数多く存在しており、発光素子の酸素や水蒸気等との接触による劣化を防ぐために発光素子は樹脂により封止されていた。
So far, there have been many light emitting devices equipped with light emitting elements such as LEDs (Light Emitting Diodes), and the light emitting elements have been sealed with a resin in order to prevent deterioration of the light emitting elements due to contact with oxygen, water vapor, or the like. ..
例えば非特許文献１には、ＣＦ3末端を有するパーフルオロ（４－ビニルオキシ－１－ブテン）（ＢＶＥ）系重合体は深紫外線に対する耐久性に優れるため、深紫外ＡｌＧａＮ系ＬＥＤの封止に用いることができることが記載されている。また特許文献１には、非晶質フッ素樹脂により紫外線発光素子が封止された紫外線発光装置が開示されている。更に特許文献２には、テトラフルオロエチレン（ＴＦＥ）、ヘキサフルオロプロピレン（ＨＦＰ）及びビニリデンフルオライド（ＶｄＦ）を少なくとも含むフッ素ポリマー（ＴＨＶ）をＬＥＤ素子の封止に用いることが開示されている。更に特許文献３には、フッ素樹脂と熱伝導率が１．５Ｗ／ｍＫ以上である熱伝導材とを含有する樹脂組成物は波長変換部材や封止部材等に好適に用いられることが記載されている。
For example, in Non-Patent Document 1, a perfluoro (4-vinyloxy-1-butene) (BVE) polymer having a CF 3 terminal is used for encapsulating a deep ultraviolet AlGaN LED because it has excellent durability against deep ultraviolet rays. It is stated that it can be done. Further, Patent Document 1 discloses an ultraviolet light emitting device in which an ultraviolet light emitting element is sealed with an amorphous fluororesin. Further, Patent Document 2 discloses that a fluoropolymer (THV) containing at least tetrafluoroethylene (TFE), hexafluoropropylene (HFP) and vinylidene fluoride (VdF) is used for encapsulating an LED element. Further, Patent Document 3 describes that a resin composition containing a fluororesin and a heat conductive material having a thermal conductivity of 1.5 W / mK or more is suitably used for a wavelength conversion member, a sealing member, and the like. ing.
上記の通り、これまでに発光素子を樹脂により封止する技術は種々知られており、特に紫外線発光素子を封止するに当たっては、紫外線に対する耐久性の高いフッ素樹脂を含有する組成物が用いられている。このようなフッ素樹脂含有組成物には、紫外線に対する耐久性のみならず、紫外線発光素子の発熱に対する耐熱性の向上や、紫外線発光装置の基材等に対する密着性等の向上も期待されている。本発明は、上記事情に鑑みてなされたものであり、その目的は、耐熱性および密着性に優れた樹脂組成物を提供することにある。また本発明の他の目的は、封止部の耐熱性および密着性に優れた紫外線発光装置を提供することにある。
As described above, various techniques for sealing a light emitting element with a resin have been known so far, and particularly when sealing an ultraviolet light emitting element, a composition containing a fluororesin having high durability against ultraviolet rays is used. ing. Such a fluororesin-containing composition is expected to improve not only the durability against ultraviolet rays but also the heat resistance of the ultraviolet light emitting element against heat generation and the adhesion of the ultraviolet light emitting device to the base material and the like. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition having excellent heat resistance and adhesion. Another object of the present invention is to provide an ultraviolet light emitting device having excellent heat resistance and adhesion of a sealing portion.
上記課題を解決することのできた本発明の樹脂組成物、および紫外線発光装置は、以下の構成からなる。
［１］フッ素樹脂、及び無機フィラーを含み、
上記フッ素樹脂は、テトラフルオロエチレン由来の構成単位Ａ、ヘキサフルオロプロピレン由来の構成単位Ｂ、及びフッ化ビニリデン由来の構成単位Ｃを含み、
上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ａのモル比（Ａ）が０．２５以上であり、
上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ｃのモル比（Ｃ）が０．６０以下であることを特徴とする樹脂組成物。
［２］上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ａのモル比（Ａ）が０．２５以上、０．７５以下である［１］に記載の樹脂組成物。
［３］上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ｃのモル比（Ｃ）が０．２０以上、０．６０以下である［１］または［２］に記載の樹脂組成物。
［４］上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ｂのモル比（Ｂ）が０．０５以上、０．５０以下である［１］～［３］のいずれかに記載の樹脂組成物。
［５］上記モル比（Ｃ）の上記モル比（Ａ）に対する比（モル比（Ｃ）／モル比（Ａ））が０．２０以上、３．５０以下である［３］に記載の樹脂組成物。
［６］上記モル比（Ｂ）の上記モル比（Ａ）に対する比（モル比（Ｂ）／モル比（Ａ））が０．１０以上、０．８０以下である［４］に記載の樹脂組成物。
［７］上記無機フィラーが金属フッ化物である［１］～［６］のいずれかに記載の樹脂組成物。
［８］上記無機フィラーの粒径が３００μｍ以下である［１］～［７］のいずれかに記載の樹脂組成物。
［９］上記フッ素樹脂、及び上記無機フィラーの合計１００質量部に対する上記無機フィラーの量が１質量部以上、６０質量部以下である［１］～［８］のいずれかに記載の樹脂組成物。
［１０］上記フッ素樹脂と上記無機フィラーとの屈折率の差が０．０５以下である［１］～［９］のいずれかに記載の樹脂組成物。
［１１］紫外線発光素子の封止に用いられるものである［１］～［１０］のいずれかに記載の樹脂組成物。
［１２］紫外線発光素子を備え、
上記紫外線発光素子が、［１］～［１１］のいずれかに記載の樹脂組成物の固化物により封止されていることを特徴とする紫外線発光装置。 The resin composition of the present invention and the ultraviolet light emitting device capable of solving the above problems have the following configurations.
[1] Contains fluororesin and inorganic filler
The fluororesin contains a constituent unit A derived from tetrafluoroethylene, a constituent unit B derived from hexafluoropropylene, and a constituent unit C derived from vinylidene fluoride.
The molar ratio (A) of the structural unit A to the total of the structural unit A, the structural unit B, and the structural unit C is 0.25 or more.
A resin composition, wherein the molar ratio (C) of the structural unit C to the total of the structural unit A, the structural unit B, and the structural unit C is 0.60 or less.
[2] The resin according to [1], wherein the molar ratio (A) of the structural unit A to the total of the structural unit A, the structural unit B, and the structural unit C is 0.25 or more and 0.75 or less. Composition.
[3] The molar ratio (C) of the structural unit C to the total of the structural unit A, the structural unit B, and the structural unit C is 0.20 or more and 0.60 or less [1] or [2]. The resin composition according to.
[4] The molar ratio (B) of the structural unit B to the total of the structural unit A, the structural unit B, and the structural unit C is 0.05 or more and 0.50 or less [1] to [3]. The resin composition according to any one of.
[5] The resin according to [3], wherein the ratio of the molar ratio (C) to the molar ratio (A) (molar ratio (C) / molar ratio (A)) is 0.20 or more and 3.50 or less. Composition.
[6] The resin according to [4], wherein the ratio of the molar ratio (B) to the molar ratio (A) (molar ratio (B) / molar ratio (A)) is 0.10 or more and 0.80 or less. Composition.
[7] The resin composition according to any one of [1] to [6], wherein the inorganic filler is a metal fluoride.
[8] The resin composition according to any one of [1] to [7], wherein the inorganic filler has a particle size of 300 μm or less.
[9] The resin composition according to any one of [1] to [8], wherein the amount of the inorganic filler is 1 part by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total of the fluororesin and the inorganic filler. ..
[10] The resin composition according to any one of [1] to [9], wherein the difference in refractive index between the fluororesin and the inorganic filler is 0.05 or less.
[11] The resin composition according to any one of [1] to [10], which is used for sealing an ultraviolet light emitting element.
[12] Equipped with an ultraviolet light emitting element
An ultraviolet light emitting device, characterized in that the ultraviolet light emitting element is sealed with a solidified resin composition according to any one of [1] to [11].
［１］フッ素樹脂、及び無機フィラーを含み、
上記フッ素樹脂は、テトラフルオロエチレン由来の構成単位Ａ、ヘキサフルオロプロピレン由来の構成単位Ｂ、及びフッ化ビニリデン由来の構成単位Ｃを含み、
上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ａのモル比（Ａ）が０．２５以上であり、
上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ｃのモル比（Ｃ）が０．６０以下であることを特徴とする樹脂組成物。
［２］上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ａのモル比（Ａ）が０．２５以上、０．７５以下である［１］に記載の樹脂組成物。
［３］上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ｃのモル比（Ｃ）が０．２０以上、０．６０以下である［１］または［２］に記載の樹脂組成物。
［４］上記構成単位Ａ、上記構成単位Ｂ、及び上記構成単位Ｃの合計に対する上記構成単位Ｂのモル比（Ｂ）が０．０５以上、０．５０以下である［１］～［３］のいずれかに記載の樹脂組成物。
［５］上記モル比（Ｃ）の上記モル比（Ａ）に対する比（モル比（Ｃ）／モル比（Ａ））が０．２０以上、３．５０以下である［３］に記載の樹脂組成物。
［６］上記モル比（Ｂ）の上記モル比（Ａ）に対する比（モル比（Ｂ）／モル比（Ａ））が０．１０以上、０．８０以下である［４］に記載の樹脂組成物。
［７］上記無機フィラーが金属フッ化物である［１］～［６］のいずれかに記載の樹脂組成物。
［８］上記無機フィラーの粒径が３００μｍ以下である［１］～［７］のいずれかに記載の樹脂組成物。
［９］上記フッ素樹脂、及び上記無機フィラーの合計１００質量部に対する上記無機フィラーの量が１質量部以上、６０質量部以下である［１］～［８］のいずれかに記載の樹脂組成物。
［１０］上記フッ素樹脂と上記無機フィラーとの屈折率の差が０．０５以下である［１］～［９］のいずれかに記載の樹脂組成物。
［１１］紫外線発光素子の封止に用いられるものである［１］～［１０］のいずれかに記載の樹脂組成物。
［１２］紫外線発光素子を備え、
上記紫外線発光素子が、［１］～［１１］のいずれかに記載の樹脂組成物の固化物により封止されていることを特徴とする紫外線発光装置。 The resin composition of the present invention and the ultraviolet light emitting device capable of solving the above problems have the following configurations.
[1] Contains fluororesin and inorganic filler
The fluororesin contains a constituent unit A derived from tetrafluoroethylene, a constituent unit B derived from hexafluoropropylene, and a constituent unit C derived from vinylidene fluoride.
The molar ratio (A) of the structural unit A to the total of the structural unit A, the structural unit B, and the structural unit C is 0.25 or more.
A resin composition, wherein the molar ratio (C) of the structural unit C to the total of the structural unit A, the structural unit B, and the structural unit C is 0.60 or less.
[2] The resin according to [1], wherein the molar ratio (A) of the structural unit A to the total of the structural unit A, the structural unit B, and the structural unit C is 0.25 or more and 0.75 or less. Composition.
[3] The molar ratio (C) of the structural unit C to the total of the structural unit A, the structural unit B, and the structural unit C is 0.20 or more and 0.60 or less [1] or [2]. The resin composition according to.
[4] The molar ratio (B) of the structural unit B to the total of the structural unit A, the structural unit B, and the structural unit C is 0.05 or more and 0.50 or less [1] to [3]. The resin composition according to any one of.
[5] The resin according to [3], wherein the ratio of the molar ratio (C) to the molar ratio (A) (molar ratio (C) / molar ratio (A)) is 0.20 or more and 3.50 or less. Composition.
[6] The resin according to [4], wherein the ratio of the molar ratio (B) to the molar ratio (A) (molar ratio (B) / molar ratio (A)) is 0.10 or more and 0.80 or less. Composition.
[7] The resin composition according to any one of [1] to [6], wherein the inorganic filler is a metal fluoride.
[8] The resin composition according to any one of [1] to [7], wherein the inorganic filler has a particle size of 300 μm or less.
[9] The resin composition according to any one of [1] to [8], wherein the amount of the inorganic filler is 1 part by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the total of the fluororesin and the inorganic filler. ..
[10] The resin composition according to any one of [1] to [9], wherein the difference in refractive index between the fluororesin and the inorganic filler is 0.05 or less.
[11] The resin composition according to any one of [1] to [10], which is used for sealing an ultraviolet light emitting element.
[12] Equipped with an ultraviolet light emitting element
An ultraviolet light emitting device, characterized in that the ultraviolet light emitting element is sealed with a solidified resin composition according to any one of [1] to [11].
本発明によれば、上記構成により、耐熱性および密着性に優れた樹脂組成物、及び封止部の耐熱性および密着性に優れた紫外線発光装置を得ることができる。
According to the present invention, it is possible to obtain a resin composition having excellent heat resistance and adhesion and an ultraviolet light emitting device having excellent heat resistance and adhesion of the sealing portion by the above configuration.
本発明の樹脂組成物は、フッ素樹脂、及び無機フィラーを含み、フッ素樹脂は、テトラフルオロエチレン由来の構成単位Ａ、ヘキサフルオロプロピレン由来の構成単位Ｂ、及びフッ化ビニリデン由来の構成単位Ｃを含み、構成単位Ａ、構成単位Ｂ、及び構成単位Ｃの合計に対する構成単位Ａのモル比（Ａ）が０．２５以上であり、構成単位Ａ、構成単位Ｂ、及び構成単位Ｃの合計に対する構成単位Ｃのモル比（Ｃ）が０．６０以下である点に特徴を有する。これにより紫外線発光素子の発熱に対する耐熱性、および紫外線発光装置の基材等に対する密着性を向上することができる。以下では、フッ素樹脂、及び無機フィラーの詳細について順に説明する。
The resin composition of the present invention contains a fluorine resin and an inorganic filler, and the fluorine resin contains a constitutional unit A derived from tetrafluoroethylene, a constitutional unit B derived from hexafluoropropylene, and a constitutional unit C derived from vinylidene fluoride. , The molar ratio (A) of the constituent unit A to the total of the constituent unit A, the constituent unit B, and the constituent unit C is 0.25 or more, and the constituent unit with respect to the total of the constituent unit A, the constituent unit B, and the constituent unit C. It is characterized in that the molar ratio (C) of C is 0.60 or less. This makes it possible to improve the heat resistance of the ultraviolet light emitting element to heat generation and the adhesion of the ultraviolet light emitting device to the base material and the like. Hereinafter, the details of the fluororesin and the inorganic filler will be described in order.
以下では、テトラフルオロエチレン由来の構成単位Ａ、ヘキサフルオロプロピレン由来の構成単位Ｂ、及びフッ化ビニリデン由来の構成単位Ｃを含み、構成単位Ａ、構成単位Ｂ、及び構成単位Ｃの合計に対する構成単位Ａのモル比（Ａ）が０．２５以上であり、構成単位Ａ、構成単位Ｂ、及び構成単位Ｃの合計に対する構成単位Ｃのモル比（Ｃ）が０．６０以下であるフッ素樹脂を、本発明のフッ素樹脂と呼ぶ場合がある。
In the following, a structural unit A derived from tetrafluoroethylene, a structural unit B derived from hexafluoropropylene, and a structural unit C derived from vinylidene fluoride are included, and a structural unit with respect to the total of the structural unit A, the structural unit B, and the structural unit C. A fluorine resin having a molar ratio (A) of A of 0.25 or more and a molar ratio (C) of the structural unit C to the total of the structural unit A, the structural unit B, and the structural unit C of 0.60 or less. It may be called the fluororesin of the present invention.
構成単位Ａ、構成単位Ｂ、及び構成単位Ｃの合計に対する構成単位Ａのモル比（Ａ）は０．２５以上である。これにより密着性が向上する傾向となる。そのため構成単位Ａのモル比（Ａ）の下限は、より好ましくは０．２８以上、更に好ましくは０．３０以上である。一方、構成単位Ａのモル比（Ａ）の上限は、透明性の観点から好ましくは０．７５以下、より好ましくは０．６０以下、更に好ましくは０．５０以下である。
The molar ratio (A) of the constituent unit A to the total of the constituent unit A, the constituent unit B, and the constituent unit C is 0.25 or more. This tends to improve the adhesion. Therefore, the lower limit of the molar ratio (A) of the structural unit A is more preferably 0.28 or more, still more preferably 0.30 or more. On the other hand, the upper limit of the molar ratio (A) of the constituent unit A is preferably 0.75 or less, more preferably 0.60 or less, still more preferably 0.50 or less from the viewpoint of transparency.
構成単位Ａ、構成単位Ｂ、及び構成単位Ｃの合計に対する構成単位Ｃのモル比（Ｃ）は０．６０以下である。これにより密着性が向上する傾向となる。そのため構成単位Ｃのモル比（Ｃ）の上限は、好ましくは０．５８以下、より好ましくは０．５６以下である。一方、構成単位Ｃのモル比（Ｃ）の下限は、好ましくは０．２０以上である。これにより、有機溶媒に対する溶解性が向上するため、紫外線発光素子を封止するに当たって樹脂組成物の塗布回数を低減することができる。そのため構成単位Ｃのモル比（Ｃ）の下限は、より好ましくは０．３０以上、更に好ましくは０．４０以上、更により好ましくは０．５０以上である。
The molar ratio (C) of the constituent unit C to the total of the constituent unit A, the constituent unit B, and the constituent unit C is 0.60 or less. This tends to improve the adhesion. Therefore, the upper limit of the molar ratio (C) of the structural unit C is preferably 0.58 or less, more preferably 0.56 or less. On the other hand, the lower limit of the molar ratio (C) of the structural unit C is preferably 0.20 or more. As a result, the solubility in an organic solvent is improved, so that the number of times the resin composition is applied can be reduced when sealing the ultraviolet light emitting element. Therefore, the lower limit of the molar ratio (C) of the structural unit C is more preferably 0.30 or more, still more preferably 0.40 or more, and even more preferably 0.50 or more.
構成単位Ａ、構成単位Ｂ、及び構成単位Ｃの合計に対する構成単位Ｂのモル比（Ｂ）は０．０５以上、０．５０以下であることが好ましい。構成単位Ｂのモル比（Ｂ）の下限は溶解性の観点から、より好ましくは０．０７以上、更に好ましくは０．０９以上である。一方、構成単位Ｂのモル比（Ｂ）の上限は、耐熱性の観点からより好ましくは０．４０以下、更に好ましくは０．３０以下、更により好ましくは０．２０以下である。
The molar ratio (B) of the structural unit B to the total of the structural unit A, the structural unit B, and the structural unit C is preferably 0.05 or more and 0.50 or less. The lower limit of the molar ratio (B) of the structural unit B is more preferably 0.07 or more, still more preferably 0.09 or more, from the viewpoint of solubility. On the other hand, the upper limit of the molar ratio (B) of the constituent unit B is more preferably 0.40 or less, still more preferably 0.30 or less, still more preferably 0.20 or less from the viewpoint of heat resistance.
モル比（Ｃ）のモル比（Ａ）に対する比（モル比（Ｃ）／モル比（Ａ））は、０．２０以上、３．５０以下であることが好ましい。モル比（Ｃ）／モル比（Ａ）を上記範囲に制御することによって、密着性が向上する傾向となる。また、高温加熱時の樹脂の着色を防止できる。モル比（Ｃ）／モル比（Ａ）の下限は、より好ましくは０．５０以上、更に好ましくは１．００以上、更により好ましくは１.３０以上、特に好ましくは１．４５以上、最も好ましくは１．５０以上である。一方、モル比（Ｃ）／モル比（Ａ）の上限は、より好ましくは３．００以下、更に好ましくは２．５０以下、更により好ましくは２．００以下である。
The ratio of the molar ratio (C) to the molar ratio (A) (molar ratio (C) / molar ratio (A)) is preferably 0.20 or more and 3.50 or less. By controlling the molar ratio (C) / molar ratio (A) within the above range, the adhesion tends to be improved. In addition, coloring of the resin during high-temperature heating can be prevented. The lower limit of the molar ratio (C) / molar ratio (A) is more preferably 0.50 or more, still more preferably 1.00 or more, even more preferably 1.30 or more, particularly preferably 1.45 or more, most preferably. Is 1.50 or more. On the other hand, the upper limit of the molar ratio (C) / molar ratio (A) is more preferably 3.00 or less, still more preferably 2.50 or less, and even more preferably 2.00 or less.
モル比（Ｂ）のモル比（Ａ）に対する比（モル比（Ｂ）／モル比（Ａ））は、０．１０以上、０．８０以下であることが好ましい。モル比（Ｂ）／モル比（Ａ）を上記範囲に制御することにより、密着性が向上する傾向となる。モル比（Ｂ）／モル比（Ａ）の下限は、より好ましくは０．２０以上、更に好ましくは０．２４以上、更により好ましくは０．２８以上である。一方、モル比（Ｂ）／モル比（Ａ）の上限は、より好ましくは０．６０以下、更に好ましくは０．５０以下、更により好ましくは０．４０以下である。
The ratio of the molar ratio (B) to the molar ratio (A) (molar ratio (B) / molar ratio (A)) is preferably 0.10 or more and 0.80 or less. By controlling the molar ratio (B) / molar ratio (A) within the above range, the adhesion tends to be improved. The lower limit of the molar ratio (B) / molar ratio (A) is more preferably 0.20 or more, still more preferably 0.24 or more, and even more preferably 0.28 or more. On the other hand, the upper limit of the molar ratio (B) / molar ratio (A) is more preferably 0.60 or less, still more preferably 0.50 or less, and even more preferably 0.40 or less.
フッ素樹脂の各構成単位のモル比は、後記する実施例に記載のＮＭＲ測定により求めることができる。モル比の算出に当たっては、例えばEric B. Twum et al., “Multidimensional 19F NMR Analyses of Terpolymers from Vinylidene Fluoride (VDF)-Hexafluoropropylene (HFP)-Tetrafluoroethylene (TFE)”, Macromolecules、2015年、48巻、11号、p.3563-3576を参照することができる。
The molar ratio of each constituent unit of the fluororesin can be obtained by the NMR measurement described in Examples described later. In calculating the molar ratio, for example, Eric B. Twum et al., “Multidimensional 19F NMR Analyses of Terpolymers from Vinylidene Fluoride (VDF) -Hexafluoropropylene (HFP) -Tetrafluoroethylene (TFE)”, Macromolecules, Vol. No., p.3563-3576 can be referred to.
本発明のフッ素樹脂は、テトラフルオロエチレン由来の構成単位Ａ、ヘキサフルオロプロピレン由来の構成単位Ｂ、及びフッ化ビニリデン由来の構成単位Ｃを含むものであるが、構成単位Ａ、構成単位Ｂ、及び構成単位Ｃ以外の他の構成単位を含んでいてもよい。他の構成単位としては、例えばエチレン由来の構成単位、パーフルオロアルキルビニルエーテル由来の構成単位、クロロトリフルオロエチレン由来の構成単位等が挙げられる。
The fluororesin of the present invention contains a constituent unit A derived from tetrafluoroethylene, a constituent unit B derived from hexafluoropropylene, and a constituent unit C derived from vinylidene fluoride, but the constituent unit A, the constituent unit B, and the constituent unit It may include other structural units other than C. Examples of other structural units include ethylene-derived structural units, perfluoroalkyl vinyl ether-derived structural units, and chlorotrifluoroethylene-derived structural units.
本発明のフッ素樹脂の屈折率は、好ましくは１．３４超、より好ましくは１．３５以上、更に好ましくは１．３６以上である。これにより、後述する紫外線発光素子と封止部の屈折率の差を小さくすることができ、紫外線発光素子と封止部との界面における全反射を低減して、光取出し効率を向上させることができる。なお光取出し効率とは、紫外線発光素子で発生した光が紫外線発光素子の外部に取り出される効率のことである。一方、本発明のフッ素樹脂の屈折率の上限は、例えば１．４５以下であり、１．４０以下であってもよい。屈折率は、カタログ値や一般的な物性表に記載の数値を使用してもよいし、市販のアッベ屈折率計又はエリプソメーターなどを使用して後記する実施例に記載の方法により測定することもできる。なお本願で記載する屈折率は、一般的に用いられるナトリウムのＤ線（５８９ｎｍ）の波長における値である。
The refractive index of the fluororesin of the present invention is preferably more than 1.34, more preferably 1.35 or more, still more preferably 1.36 or more. As a result, the difference in the refractive index between the ultraviolet light emitting element and the sealing portion, which will be described later, can be reduced, the total reflection at the interface between the ultraviolet emitting element and the sealing portion can be reduced, and the light extraction efficiency can be improved. it can. The light extraction efficiency is the efficiency at which the light generated by the ultraviolet light emitting element is extracted to the outside of the ultraviolet light emitting element. On the other hand, the upper limit of the refractive index of the fluororesin of the present invention is, for example, 1.45 or less, and may be 1.40 or less. The refractive index may be a value described in a catalog value or a general physical property table, or may be measured by a method described in Examples described later using a commercially available Abbe refractive index meter or ellipsometer. You can also. The refractive index described in the present application is a value at the wavelength of the commonly used sodium D line (589 nm).
本発明のフッ素樹脂の全構成単位に対する構成単位Ａ、構成単位Ｂ、及び構成単位Ｃの合計モル比は、好ましくは０．７０以上、より好ましくは０．８０以上、更に好ましくは０．９０以上、特に好ましくは０．９５以上、最も好ましくは１である。即ち本発明のフッ素樹脂の全構成単位が構成単位Ａ、構成単位Ｂ、及び構成単位Ｃからなることが最も好ましい。これにより、密着性が向上する傾向となる。
The total molar ratio of the constituent unit A, the constituent unit B, and the constituent unit C to all the constituent units of the fluororesin of the present invention is preferably 0.70 or more, more preferably 0.80 or more, still more preferably 0.90 or more. , Especially preferably 0.95 or more, and most preferably 1. That is, it is most preferable that all the constituent units of the fluororesin of the present invention are composed of the constituent unit A, the constituent unit B, and the constituent unit C. As a result, the adhesion tends to be improved.
本発明のフッ素樹脂の重量平均分子量は５０，０００以上、１，０００，０００以下であることが好ましい。重量平均分子量を５０，０００以上とすることにより融解時の粘度を高くすることができるため、ＬＥＤ点灯時の封止樹脂の形状変化を抑制することができる。本発明のフッ素樹脂の重量平均分子量の下限は、より好ましくは１００，０００以上、更に好ましくは２００，０００以上、更により好ましくは２５０，０００以上、特に好ましくは３００，０００以上である。一方、本発明のフッ素樹脂の重量平均分子量を１，０００，０００以下とすることにより溶解性が良くなる。本発明のフッ素樹脂の重量平均分子量の上限は、より好ましくは８００，０００以下、更に好ましくは５００，０００以下、更により好ましくは４５０，０００以下、特に好ましくは４００，０００以下である。なお、重量平均分子量は標準ポリスチレン換算値である。
The weight average molecular weight of the fluororesin of the present invention is preferably 50,000 or more and 1,000,000 or less. By setting the weight average molecular weight to 50,000 or more, the viscosity at the time of melting can be increased, so that the shape change of the sealing resin at the time of lighting the LED can be suppressed. The lower limit of the weight average molecular weight of the fluororesin of the present invention is more preferably 100,000 or more, still more preferably 200,000 or more, still more preferably 250,000 or more, and particularly preferably 300,000 or more. On the other hand, the solubility is improved by setting the weight average molecular weight of the fluororesin of the present invention to 1,000,000 or less. The upper limit of the weight average molecular weight of the fluororesin of the present invention is more preferably 800,000 or less, still more preferably 500,000 or less, even more preferably 450,000 or less, and particularly preferably 400,000 or less. The weight average molecular weight is a standard polystyrene conversion value.
本発明のフッ素樹脂は、ランダム共重合体、またはブロック共重合体のいずれであってもよいが、ランダム共重合体であることが好ましい。これにより、構成単位Ａや構成単位Ｃの結晶化度を抑制することができ、透明性を確保しやすい。
The fluororesin of the present invention may be either a random copolymer or a block copolymer, but is preferably a random copolymer. As a result, the crystallinity of the structural unit A and the structural unit C can be suppressed, and transparency can be easily ensured.
本発明のフッ素樹脂は、融点が９０℃以上、２７８℃以下であることが好ましい。融点が９０℃以上であることにより、紫外線発光素子の発熱による本発明のフッ素樹脂の溶融を防止し易くすることができる。本発明のフッ素樹脂の融点の下限は、より好ましくは１００℃以上、更に好ましくは１１０℃以上、更により好ましくは１１５℃以上である。一方、融点が２７８℃以下であることにより、本発明のフッ素樹脂は加熱溶融し易くなるため、加熱溶融による紫外線発光素子の封止を行い易くすることができる。更に一般的なハンダ材であるＡｕ－Ｓｎ（２０質量％）の融点が２７８℃であることから、樹脂の融点が２７８℃以下であることにより、加熱に伴う後述のバンプの溶融を防止し易くすることができる。本発明のフッ素樹脂の融点の上限は、より好ましくは２００℃以下、更に好ましくは１７０℃以下、更により好ましくは１５０℃以下、特に好ましくは１３０℃以下である。本発明のフッ素樹脂の融点は、カタログ値を用いても良いし、例えば示差走査熱量計（ＤＳＣ、日立ハイテクサイエンス社製）を用いて、昇温速度１０℃／分で－５０℃から２００℃の温度まで変化させ、これにより得られる融解曲線から融解ピーク温度（Ｔｍ）を測定することにより求めることができる。
The fluororesin of the present invention preferably has a melting point of 90 ° C. or higher and 278 ° C. or lower. When the melting point is 90 ° C. or higher, it is possible to easily prevent the fluororesin of the present invention from melting due to heat generation of the ultraviolet light emitting element. The lower limit of the melting point of the fluororesin of the present invention is more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and even more preferably 115 ° C. or higher. On the other hand, when the melting point is 278 ° C. or lower, the fluororesin of the present invention is easily melted by heating, so that the ultraviolet light emitting element can be easily sealed by heating and melting. Further, since the melting point of Au-Sn (20% by mass), which is a general solder material, is 278 ° C., the melting point of the resin is 278 ° C. or less, so that it is easy to prevent the bumps described later from melting due to heating. can do. The upper limit of the melting point of the fluororesin of the present invention is more preferably 200 ° C. or lower, still more preferably 170 ° C. or lower, still more preferably 150 ° C. or lower, and particularly preferably 130 ° C. or lower. For the melting point of the fluororesin of the present invention, a catalog value may be used, or for example, using a differential scanning calorimeter (DSC, manufactured by Hitachi High-Tech Science Co., Ltd.), the temperature rise rate is 10 ° C./min and the temperature is -50 ° C. to 200 ° C. It can be obtained by changing the temperature to the above temperature and measuring the melting peak temperature (Tm) from the melting curve obtained thereby.
無機フィラーとして、金属フッ化物、金属酸化物、金属リン酸塩、金属炭酸塩、金属スルホン酸塩、金属硝酸塩、金属窒化物、窒化ホウ素等が挙げられる。無機フィラーは、１種で用いてもよいし、２種以上を併用してもよい。無機フィラーと本発明のフッ素樹脂とを組み合わせることにより、無機フィラーが本発明のフッ素樹脂の熱分解を防止し易くするという効果を発揮することができる。
Examples of the inorganic filler include metal fluoride, metal oxide, metal phosphate, metal carbonate, metal sulfonate, metal nitrate, metal nitride, boron nitride and the like. The inorganic filler may be used alone or in combination of two or more. By combining the inorganic filler and the fluororesin of the present invention, the effect that the inorganic filler facilitates the prevention of thermal decomposition of the fluororesin of the present invention can be exhibited.
無機フィラーは、熱分解の防止と透明性の観点から金属フッ化物であることが好ましい。金属フッ化物として、フッ化カルシウム、フッ化バリウム、フッ化ストロンチウム、フッ化リチウム、フッ化ナトリウム、フッ化マグネシウム、氷晶石等が挙げられる。このうちフッ化マグネシウムが好ましい。これらは１種で用いてもよいし、２種以上を併用してもよい。無機フィラーは、多結晶体であっても単結晶体であってもよいが、粒界での光の散乱を少なくすることにより樹脂成形体の光透過性を向上しやすくする観点、又は樹脂成形体における無機フィラーの凝集を抑制し樹脂成形体の光透過性を向上しやすくする観点からは、粒子中に含まれる粒界が少ない方が好ましく、単結晶体を用いることが特に好ましい。無機フィラーが単結晶体かどうかの確認は、例えば電子顕微鏡で電子線回折パターンを確認することで判断することができる。
The inorganic filler is preferably a metal fluoride from the viewpoint of preventing thermal decomposition and transparency. Examples of the metal fluoride include calcium fluoride, barium fluoride, strontium fluoride, lithium fluoride, sodium fluoride, magnesium fluoride, glacial stone and the like. Of these, magnesium fluoride is preferable. These may be used alone or in combination of two or more. The inorganic filler may be a polycrystalline body or a single crystal body, but from the viewpoint of facilitating the improvement of the light transmittance of the resin molded body by reducing the scattering of light at the grain boundaries, or the resin molding. From the viewpoint of suppressing the aggregation of the inorganic filler in the body and facilitating the improvement of the light transmittance of the resin molded body, it is preferable that the grain boundaries contained in the particles are small, and it is particularly preferable to use a single crystal. Whether or not the inorganic filler is a single crystal can be determined by, for example, confirming the electron diffraction pattern with an electron microscope.
無機フィラーの粒径は３００μｍ以下であることが好ましい。無機フィラーが３００μｍ以下であることにより樹脂組成物の温度上昇に伴う変色を低減することができる。無機フィラーの粒径は、より好ましくは２００μｍ以下、更に好ましくは１００μｍ以下、更により好ましくは５０μｍ以下、殊更好ましくは３０μｍ以下、特に好ましくは２０μｍ以下である。一方、無機フィラーの粒径は０．５μｍ以上であることが好ましい。無機フィラーの粒径を０．５μｍ以上とすることにより樹脂とフィラー間での光の散乱を抑えることができ、樹脂の透明性が優れる。無機フィラーの粒径の下限は、より好ましくは１μｍ以上、更に好ましくは５μｍ以上である。この無機フィラーの粒径とは、レーザー回析法による体積累積頻度５０％の粒径Ｄ50である。
The particle size of the inorganic filler is preferably 300 μm or less. When the inorganic filler is 300 μm or less, discoloration due to an increase in temperature of the resin composition can be reduced. The particle size of the inorganic filler is more preferably 200 μm or less, still more preferably 100 μm or less, even more preferably 50 μm or less, particularly preferably 30 μm or less, and particularly preferably 20 μm or less. On the other hand, the particle size of the inorganic filler is preferably 0.5 μm or more. By setting the particle size of the inorganic filler to 0.5 μm or more, it is possible to suppress light scattering between the resin and the filler, and the transparency of the resin is excellent. The lower limit of the particle size of the inorganic filler is more preferably 1 μm or more, still more preferably 5 μm or more. The particle size of this inorganic filler is a particle size D 50 having a volume accumulation frequency of 50% by a laser diffraction method.
本発明のフッ素樹脂と無機フィラーとの屈折率の差は、０．０５以下であることが好ましい。このように屈折率の差を低減することにより、無機フィラーの表面（組成物中における、無機フィラーの表面とフッ素樹脂との界面）での光の散乱を抑制できるため、光取出し効率を向上することができる。本発明のフッ素樹脂と無機フィラーとの屈折率の差は、より好ましくは０．０４以下、更に好ましくは０．０３以下であることが更により好ましい。一方、本発明のフッ素樹脂と無機フィラーとの屈折率の差の下限は特に限定されないが例えば０．００１以上であってもよい。本発明の無機フィラーの屈折率は、カタログ値や一般的な物性表に記載の数値を使用しても良いし、アッベ屈折率計、エリプソメーターなど後記する実施例に記載の方法により測定することができる。
The difference in refractive index between the fluororesin of the present invention and the inorganic filler is preferably 0.05 or less. By reducing the difference in refractive index in this way, it is possible to suppress light scattering on the surface of the inorganic filler (the interface between the surface of the inorganic filler and the fluororesin in the composition), thereby improving the light extraction efficiency. be able to. The difference in refractive index between the fluororesin of the present invention and the inorganic filler is more preferably 0.04 or less, still more preferably 0.03 or less. On the other hand, the lower limit of the difference in refractive index between the fluororesin of the present invention and the inorganic filler is not particularly limited, but may be, for example, 0.001 or more. The refractive index of the inorganic filler of the present invention may be a value described in a catalog value or a general physical property table, or may be measured by a method described in Examples described later such as an Abbe refractive index meter and an ellipsometer. Can be done.
無機フィラーの比表面積（１ｇあたりの表面積）は３０ｍ2／ｇ以下であることが好ましい。このように比表面積を低減することにより、樹脂組成物の着色を抑制することができ、特に紫外領域の透過性に優れる樹脂組成物を得ることができる。比表面積は、より好ましくは２０ｍ2／ｇ以下であり、更に好ましくは１０ｍ2／ｇで以下あり、殊更好ましくは５ｍ2／ｇ以下であり、特に好ましくは３ｍ2／ｇ以下であり、また０．１ｍ2／ｇ以上であってもよく、０．５ｍ2／ｇ以上であってもよい。無機フィラーの比表面積は例えば、ＢＥＴ法を用いた比表面積測定方法を用いることができる。
The specific surface area (surface area per 1 g) of the inorganic filler is preferably 30 m 2 / g or less. By reducing the specific surface area in this way, coloring of the resin composition can be suppressed, and a resin composition having particularly excellent permeability in the ultraviolet region can be obtained. The specific surface area is more preferably 20 m 2 / g or less, further preferably 10 m 2 / g or less, particularly preferably 5 m 2 / g or less, particularly preferably 3 m 2 / g or less, and 0. it may also be .1m 2 / g or more, may be 0.5 m 2 / g or more. For the specific surface area of the inorganic filler, for example, a method for measuring the specific surface area using the BET method can be used.
本発明のフッ素樹脂、及び無機フィラーの合計１００質量部に対する無機フィラーの量は１質量部以上、６０質量部以下であることが好ましい。無機フィラーの量が１質量部以上であることにより、フッ素樹脂の熱分解を防止し易くすることができる。そのため無機フィラーの量の下限は、より好ましくは１０質量部以上、更に好ましくは１５質量部以上、更により好ましくは２０質量部以上、特に好ましくは２５質量部以上である。一方、無機フィラーの量が６０質量部以下であることにより、本発明のフッ素樹脂の密着性が発揮され易くなる。そのため無機フィラーの量の上限は、より好ましくは５０質量部以下、更に好ましくは４５質量部以下である。
The amount of the inorganic filler with respect to a total of 100 parts by mass of the fluororesin and the inorganic filler of the present invention is preferably 1 part by mass or more and 60 parts by mass or less. When the amount of the inorganic filler is 1 part by mass or more, it is possible to easily prevent thermal decomposition of the fluororesin. Therefore, the lower limit of the amount of the inorganic filler is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more. On the other hand, when the amount of the inorganic filler is 60 parts by mass or less, the adhesion of the fluororesin of the present invention is easily exhibited. Therefore, the upper limit of the amount of the inorganic filler is more preferably 50 parts by mass or less, still more preferably 45 parts by mass or less.
本発明のフッ素樹脂、及び無機フィラーの合計１００質量部に対する本発明のフッ素樹脂の量は４０質量部以上、９９質量部以下であることが好ましい。本発明のフッ素樹脂の量が４０質量部以上であることにより、本発明のフッ素樹脂の密着性が発揮され易くなる。そのため本発明のフッ素樹脂の量の下限は、より好ましくは５０質量部以上、更に好ましくは５５質量部以上である。一方、本発明のフッ素樹脂の量が９９質量部以下であることにより、無機フィラーによる耐熱性向上効果が発揮され易くなる。そのため本発明のフッ素樹脂の量の上限は、より好ましくは９０質量部以下、更に好ましくは８５質量部以下である。
The amount of the fluororesin of the present invention with respect to a total of 100 parts by mass of the fluororesin of the present invention and the inorganic filler is preferably 40 parts by mass or more and 99 parts by mass or less. When the amount of the fluororesin of the present invention is 40 parts by mass or more, the adhesion of the fluororesin of the present invention can be easily exhibited. Therefore, the lower limit of the amount of the fluororesin of the present invention is more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more. On the other hand, when the amount of the fluororesin of the present invention is 99 parts by mass or less, the effect of improving the heat resistance of the inorganic filler is likely to be exhibited. Therefore, the upper limit of the amount of the fluororesin of the present invention is more preferably 90 parts by mass or less, still more preferably 85 parts by mass or less.
樹脂組成物は、本発明のフッ素樹脂と無機フィラーを混合することによって製造できる。これらの混合は、例えば、溶融混錬であってもよいし、本発明のフッ素樹脂を溶融した状態で無機フィラーと混合してもよいし、本発明のフッ素樹脂を、該フッ素樹脂を溶解又は分散する溶媒の存在下で無機フィラーと混合してもよい。樹脂組成物は、固形物であってもよいし、流動物であってもよい。流動物の場合は、溶媒を含んでいてもよい。
The resin composition can be produced by mixing the fluororesin of the present invention and an inorganic filler. These mixings may be, for example, melt kneading, or the fluororesin of the present invention may be mixed with an inorganic filler in a molten state, or the fluororesin of the present invention may be dissolved or the fluororesin may be dissolved. It may be mixed with an inorganic filler in the presence of a dispersing solvent. The resin composition may be a solid material or a fluid material. In the case of a fluid, it may contain a solvent.
溶媒として有機溶媒が挙げられる。有機溶媒として、酢酸エチル、酢酸メチル、酢酸プロピル、酢酸ブチル、プロピオン酸エチル、グリコールエーテルに酢酸基を付加したグリコールエステル等のエステル系溶媒；アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒；ジエチルエーテル、ジプロピルエーテル、ブチルエーテル、グリコールエーテル、テロラヒドロフラン等のエーテル類系溶媒；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジブチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド系溶媒；Ｎ－メチル－２－ピロリドンなどのラクタム系溶媒；等が挙げられる。このうちエステル系溶媒、ケトン系溶媒、エーテル系溶媒が好ましく、エステル系溶媒がより好ましい。これら有機溶媒は１種で用いてもよいし、２種以上を併用してもよい。
Examples of the solvent include organic solvents. As an organic solvent, an ester solvent such as ethyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl propionate, glycol ester obtained by adding an acetate group to glycol ether; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone-based solvent; ether-based solvent such as diethyl ether, dipropyl ether, butyl ether, glycol ether, terrorahydrofuran; amide-based solvent such as N, N-dimethylformamide, N, N-dibutylformamide, N, N-dimethylacetamide Solvents; lactam solvents such as N-methyl-2-pyrrolidone; and the like. Of these, ester-based solvents, ketone-based solvents, and ether-based solvents are preferable, and ester-based solvents are more preferable. These organic solvents may be used alone or in combination of two or more.
溶媒を用いる場合、本発明のフッ素樹脂１００質量部に対する溶媒の量は、好ましくは１００質量部以上、５０００質量部以下である。１００質量部以上であることにより本発明のフッ素樹脂を溶解又は分散し易くすることができる。溶媒の量は、より好ましくは２００質量部以上、更に好ましくは４００質量部以上、更により好ましくは６００質量部以上である。一方、５０００質量部以下であることにより、紫外線発光装置を封止するに当たっての塗布回数を減らすことができる。溶媒の量は、より好ましくは２０００質量部以下、更に好ましくは１２００質量部以下、更により好ましくは１０００質量部以下である。なお本発明のフッ素樹脂と溶媒の混合後、必要に応じて溶媒を揮発等によって低減してもよい。その場合、本発明のフッ素樹脂１００質量部に対する低減後の溶媒の量は、好ましくは２００質量部以下、より好ましくは１００質量部以下、更に好ましくは５０質量部以下、更により好ましくは２０質量部以下である。
When a solvent is used, the amount of the solvent with respect to 100 parts by mass of the fluororesin of the present invention is preferably 100 parts by mass or more and 5000 parts by mass or less. When the amount is 100 parts by mass or more, the fluororesin of the present invention can be easily dissolved or dispersed. The amount of the solvent is more preferably 200 parts by mass or more, further preferably 400 parts by mass or more, and even more preferably 600 parts by mass or more. On the other hand, when the amount is 5000 parts by mass or less, the number of times of coating for sealing the ultraviolet light emitting device can be reduced. The amount of the solvent is more preferably 2000 parts by mass or less, further preferably 1200 parts by mass or less, and even more preferably 1000 parts by mass or less. After mixing the fluororesin of the present invention and the solvent, the solvent may be reduced by volatilization or the like, if necessary. In that case, the amount of the solvent after reduction with respect to 100 parts by mass of the fluororesin of the present invention is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, still more preferably 20 parts by mass. It is as follows.
さらに樹脂組成物はその他に、本発明のフッ素樹脂以外の他のフッ素樹脂、添加剤等を含有していてもよい。
Further, the resin composition may also contain a fluororesin, an additive, etc. other than the fluororesin of the present invention.
他のフッ素樹脂として、結晶性フッ素樹脂が挙げられ、具体的には、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体（ＦＥＰ）、クロロトリフルオロエチレン重合体（ＰＣＴＦＥ）、本発明の上記構成単位Ａと構成単位Ｃの所定比率を満たさないテトラフルオロエチレン－ヘキサフルオロプロピレン－フッ化ビニリデン共重合体（ＴＨＶ）等が挙げられる。これら他のフッ素樹脂は、１種で用いてもよいし、２種以上を併用してもよい。
Examples of other fluororesins include crystalline fluororesins, and specifically, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and chlorotri. Examples thereof include a fluoroethylene polymer (PCTFE), a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) that does not satisfy the predetermined ratio of the constituent unit A and the constituent unit C of the present invention. These other fluororesins may be used alone or in combination of two or more.
本発明のフッ素樹脂１００質量部に対する他のフッ素樹脂の量は、好ましくは１０質量部以下、より好ましくは５質量部以下、更に好ましくは２質量部以下、特に好ましくは１質量部以下、最も好ましくは０質量部である。即ち、本発明の樹脂組成物に含まれるフッ素樹脂は、本発明のフッ素樹脂からなることが最も好ましい。これにより樹脂間の屈折率差が低減されて光取出し効率を向上することができる。
The amount of the other fluororesin with respect to 100 parts by mass of the fluororesin of the present invention is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 2 parts by mass or less, and particularly preferably 1 part by mass or less. Is 0 parts by mass. That is, the fluororesin contained in the resin composition of the present invention is most preferably made of the fluororesin of the present invention. As a result, the difference in refractive index between the resins can be reduced and the light extraction efficiency can be improved.
樹脂組成物（固形分）の総質量に対する全フッ素樹脂（本発明のフッ素樹脂と他のフッ素樹脂の合計）、及び無機フィラーの合計含量は９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９７質量％以上であることが更により好ましく、９９質量％以上であることが特に好ましい。これにより、フッ素樹脂による密着性向上効果と無機フィラーによる耐熱性向上効果が発揮され易くなる。
The total content of the total fluororesin (total of the fluororesin of the present invention and other fluororesins) and the inorganic filler with respect to the total mass of the resin composition (solid content) is preferably 90% by mass or more, preferably 95% by mass or more. Is more preferable, 97% by mass or more is even more preferable, and 99% by mass or more is particularly preferable. This makes it easier for the fluororesin to improve the adhesion and the inorganic filler to improve the heat resistance.
本発明の樹脂組成物は、例えば、融点以下に温度を下げたり、溶媒を揮発させることによって固化物（樹脂成形体）とすることができる。本発明の樹脂組成物は、紫外線に対する耐久性に優れ、かつ密着性、耐熱性にも優れているため、紫外線発光素子の封止に好適に用いることができる。
The resin composition of the present invention can be made into a solidified product (resin molded product) by, for example, lowering the temperature below the melting point or volatilizing the solvent. Since the resin composition of the present invention has excellent durability against ultraviolet rays, and also has excellent adhesion and heat resistance, it can be suitably used for sealing an ultraviolet light emitting element.
なお、樹脂組成物の耐熱性は、熱重量測定（ＴＧ測定）を行ってフッ素樹脂自体の質量が１０質量％低減したときの温度（１０％質量変化温度）を測定することで評価することができる。１０％質量変化温度は、４００℃以上であると樹脂組成物が耐熱性に優れるため好ましい。後述の実施例では、以下の条件で１０％質量変化温度を測定した。以下の条件のようにサンプリングは、温度が１℃上がる前までに少なくとも２回行われることが好ましい。所定の間隔（秒）でサンプリングを行って、フッ素樹脂の質量が１０質量％低減した時点以降の最初のサンプリングにおける温度を１０％質量変化温度とする。
＜測定条件＞
測定装置：ＴＧ／ＤＴＡ６２００（エスアイアイ・ナノテクノロジー株式会社製）
測定雰囲気：大気
昇温範囲：３０℃から５００℃
昇温速度：１０℃／分
サンプリング間隔：４秒 The heat resistance of the resin composition can be evaluated by performing thermal weight measurement (TG measurement) and measuring the temperature (10% mass change temperature) when the mass of the fluororesin itself is reduced by 10 mass%. it can. The 10% mass change temperature is preferably 400 ° C. or higher because the resin composition has excellent heat resistance. In the examples described later, the 10% mass change temperature was measured under the following conditions. Sampling is preferably performed at least twice before the temperature rises by 1 ° C. as in the following conditions. Sampling is performed at predetermined intervals (seconds), and the temperature at the first sampling after the time when the mass of the fluororesin is reduced by 10% by mass is defined as the 10% mass change temperature.
<Measurement conditions>
Measuring device: TG / DTA6200 (manufactured by SII Nanotechnology Co., Ltd.)
Measurement atmosphere: Atmosphere Temperature range: 30 ° C to 500 ° C
Temperature rise rate: 10 ° C / min Sampling interval: 4 seconds
＜測定条件＞
測定装置：ＴＧ／ＤＴＡ６２００（エスアイアイ・ナノテクノロジー株式会社製）
測定雰囲気：大気
昇温範囲：３０℃から５００℃
昇温速度：１０℃／分
サンプリング間隔：４秒 The heat resistance of the resin composition can be evaluated by performing thermal weight measurement (TG measurement) and measuring the temperature (10% mass change temperature) when the mass of the fluororesin itself is reduced by 10 mass%. it can. The 10% mass change temperature is preferably 400 ° C. or higher because the resin composition has excellent heat resistance. In the examples described later, the 10% mass change temperature was measured under the following conditions. Sampling is preferably performed at least twice before the temperature rises by 1 ° C. as in the following conditions. Sampling is performed at predetermined intervals (seconds), and the temperature at the first sampling after the time when the mass of the fluororesin is reduced by 10% by mass is defined as the 10% mass change temperature.
<Measurement conditions>
Measuring device: TG / DTA6200 (manufactured by SII Nanotechnology Co., Ltd.)
Measurement atmosphere: Atmosphere Temperature range: 30 ° C to 500 ° C
Temperature rise rate: 10 ° C / min Sampling interval: 4 seconds
更に本発明には、紫外線発光素子を備え、紫外線発光素子が上記樹脂組成物の固化物により封止されている紫外線発光装置も含まれる。以下では、紫外線発光素子、及び紫外線発光素子を備える紫外線発光装置について図１～４を参照しながら説明する。
Further, the present invention also includes an ultraviolet light emitting device including an ultraviolet light emitting element in which the ultraviolet light emitting element is sealed with a solidified product of the above resin composition. Hereinafter, the ultraviolet light emitting element and the ultraviolet light emitting device including the ultraviolet light emitting element will be described with reference to FIGS. 1 to 4.
図１は、紫外線発光素子の一例を模式的に示す断面図である。図２は、本発明の樹脂組成物の固化物により封止される前の紫外線発光装置の一例（以下、紫外線発光素子実装パッケージという場合がある）を模式的に示す断面図であり、図３は、本発明の樹脂組成物の固化物により封止された紫外線発光装置の一例を模式的に示す断面図であり、図４は、本発明の樹脂組成物の固化物により封止された紫外線発光装置の別の例を模式的に示す断面図である。
FIG. 1 is a cross-sectional view schematically showing an example of an ultraviolet light emitting element. FIG. 2 is a cross-sectional view schematically showing an example of an ultraviolet light emitting device (hereinafter, may be referred to as an ultraviolet light emitting element mounting package) before being sealed by the solidified product of the resin composition of the present invention. Is a cross-sectional view schematically showing an example of an ultraviolet light emitting device sealed with a solidified product of the resin composition of the present invention, and FIG. 4 is an ultraviolet ray sealed with a solidified product of the resin composition of the present invention. It is sectional drawing which shows another example of a light emitting device schematically.
まずは紫外線発光素子について説明する。図１の紫外線発光素子２はフリップチップタイプの素子であり、下側面の一部にアノード側のｐ電極１０を備え、該ｐ電極１０の上にｐ層１２が形成されている。更に紫外線発光素子２の下側面の別の一部に、カソード側のｎ電極１１を備え、ｎ電極１１の上にｎ層１４が形成されている。これらｎ電極１１とｎ層１４は、前記ｐ電極１０とｐ層１２よりも上方にシフトして形成されており、上方に存在するｎ層１４と下方に存在するｐ層１２との間に活性層１３が形成されている。更に上方に存在するｎ層１４のさらに上に基板１５が存在する。
First, the ultraviolet light emitting element will be explained. The ultraviolet light emitting element 2 of FIG. 1 is a flip-chip type element, has a p electrode 10 on the anode side on a part of the lower side surface, and a p layer 12 is formed on the p electrode 10. Further, another part of the lower side surface of the ultraviolet light emitting element 2 is provided with an n electrode 11 on the cathode side, and an n layer 14 is formed on the n electrode 11. The n-electrode 11 and the n-layer 14 are formed by shifting upward from the p-electrode 10 and the p-layer 12, and are active between the n-layer 14 existing above and the p-layer 12 existing below. Layer 13 is formed. The substrate 15 is further above the n-layer 14 that is further above.
ｎ層１４は、例えばＳｉ含有ＡｌＧａＮ層が挙げられる。ｐ層１２は、例えばＭｇ含有ＧａＮ層が挙げられる。このｐ層１２は、必要に応じて電子ブロック層などと積層構造にしてもよい。活性層１３は、例えばＡｌＧａＮ層が挙げられる。
Examples of the n-layer 14 include a Si-containing AlGaN layer. Examples of the p-layer 12 include a Mg-containing GaN layer. The p-layer 12 may have a laminated structure with an electron block layer or the like, if necessary. Examples of the active layer 13 include an AlGaN layer.
ｐ電極１０、ｐ層１２からｎ層１４、ｎ電極１１に向けて順方向電流を流すことにより活性層１３におけるバンドギャップエネルギに応じた発光が生じる。バンドギャップエネルギは、活性層１３の例えばＡｌＮモル分率を調整することにより、ＧａＮとＡｌＮが取り得るバンドギャップエネルギ（約３．４ｅＶと約６．２ｅＶ）の範囲内で制御することができ、発光波長が約２００ｎｍから約３６５ｎｍまでの紫外線発光を得ることができる。
By passing a forward current from the p electrode 10 and the p layer 12 toward the n layer 14 and the n electrode 11, light emission corresponding to the bandgap energy in the active layer 13 is generated. The bandgap energy can be controlled within the range of the bandgap energy (about 3.4 eV and about 6.2 eV) that GaN and AlN can take by adjusting, for example, the AlN mole fraction of the active layer 13. It is possible to obtain ultraviolet light emission having an emission wavelength of about 200 nm to about 365 nm.
紫外線発光素子２の発光ピーク波長は３００ｎｍ以下であることが好ましい。発光ピーク波長が３００ｎｍ以下であることにより殺菌効果が発揮され易くなるため、殺菌用の発光装置に紫外線発光素子２を用いることができる。発光ピーク波長は、より好ましくは２８０ｎｍ以下である。
The emission peak wavelength of the ultraviolet light emitting element 2 is preferably 300 nm or less. Since the sterilization effect is easily exhibited when the emission peak wavelength is 300 nm or less, the ultraviolet light emitting element 2 can be used as a light emitting device for sterilization. The emission peak wavelength is more preferably 280 nm or less.
なお基板１５として、サファイア基板、窒化アルミニウム基板等が挙げられる。ｐ電極１０の素材としてＮｉ／Ａｕ、ｎ電極１１の素材として、Ｔｉ／Ａｌ／Ｔｉ／Ａｕ等が挙げられる。また図示していないがｐ電極１０とｎ電極１１の間の露出面は、短絡を防止するためにＳｉＯ2等の保護絶縁膜により被覆されていても良い。
Examples of the substrate 15 include a sapphire substrate and an aluminum nitride substrate. Examples of the material of the p electrode 10 include Ni / Au, and examples of the material of the n electrode 11 include Ti / Al / Ti / Au. Although not shown, the exposed surface between the p electrode 10 and the n electrode 11 may be covered with a protective insulating film such as SiO 2 in order to prevent a short circuit.
次に紫外線発光素子実装パッケージについて説明する。図２の紫外線発光素子実装パッケージ６は、窒化アルミニウム（ＡｌＮ）、アルミナ（Ａｌ2Ｏ3）等のセラミックス等で形成された基材４を有し、この基材４上には配線（図示せず）が形成され、該配線上には、Ａｕ、Ａｕ－Ｓｎ（２０質量％）合金等の金属製のバンプ５が形成されている。そしてバンプ５を介して、配線（図示せず）と紫外線発光素子２のｐ電極１０、ｎ電極１１とがそれぞれ電気接続できるように固定されている。この紫外線発光素子実装パッケージ６を本発明の樹脂組成物の固化物で封止することで、図３、図４に示す紫外線発光装置１、１ａが形成される。
Next, the ultraviolet light emitting element mounting package will be described. The ultraviolet light emitting element mounting package 6 of FIG. 2 has a base material 4 made of ceramics such as aluminum nitride (AlN) and alumina (Al 2 O 3 ), and wiring (shown) is provided on the base material 4. , And metal bumps 5 such as Au and Au—Sn (20% by mass) alloy are formed on the wiring. The wiring (not shown) and the p-electrode 10 and n-electrode 11 of the ultraviolet light emitting element 2 are fixed so as to be electrically connected to each other via the bump 5. By sealing the ultraviolet light emitting element mounting package 6 with the solidified product of the resin composition of the present invention, the ultraviolet light emitting devices 1 and 1a shown in FIGS. 3 and 4 are formed.
図３の紫外線発光装置１は、図２に示した紫外線発光素子実装パッケージ６の紫外線発光素子２が本発明の樹脂組成物の固化物３ａで封止され、かつその表面に、シリカガラス、ホウケイ酸ガラス等で形成された集光レンズ７が形成されたものである。集光レンズ７によって光取出し効率を向上することができるが、該集光レンズ７は必ずしも設ける必要はない。
In the ultraviolet light emitting device 1 of FIG. 3, the ultraviolet light emitting element 2 of the ultraviolet light emitting element mounting package 6 shown in FIG. 2 is sealed with the solidified product 3a of the resin composition of the present invention, and silica glass and borosilicate glass are formed on the surface thereof. A condenser lens 7 made of acid glass or the like is formed. Although the light extraction efficiency can be improved by the condenser lens 7, the condenser lens 7 does not necessarily have to be provided.
図４の紫外線発光装置１ａは、本発明の樹脂組成物の固化物３ｂで形成される封止部材が上方に盛り上がって、レンズ形状になっている点で図３の紫外線発光装置１と異なる。
The ultraviolet light emitting device 1a of FIG. 4 is different from the ultraviolet light emitting device 1 of FIG. 3 in that the sealing member formed of the solidified product 3b of the resin composition of the present invention is raised upward to form a lens shape.
図３や図４の紫外線発光装置１、１ａの封止は、本発明の樹脂組成物を適当な溶媒に溶解した溶液を塗布、乾燥する工程を１回以上繰り返すことによって行うことができる。溶媒としては、例えば、アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトンなどのケトン系溶媒、酢酸メチル、酢酸エチル、酢酸ブチルなどのエステル系溶媒、テトラヒドロフランなどの環状エーテル、Ｎ－メチル－２－ピロリドンなどのラクタム類が挙げられる。
The ultraviolet light emitting devices 1 and 1a of FIGS. 3 and 4 can be sealed by repeating the steps of applying and drying a solution of the resin composition of the present invention in an appropriate solvent one or more times. Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate and butyl acetate, cyclic ethers such as tetrahydrofuran, N-methyl-2-pyrrolidone and the like. Lactams are mentioned.
塗布液中の樹脂組成物の濃度は、例えば、１質量％以上である。濃度を高くするほど、塗布回数を減らすことができる。好ましい濃度は５質量％以上であり、より好ましくは７質量％以上である。また前記濃度は、例えば、５０質量％以下である。濃度を低くするほど、塗布液の粘性の向上を防ぐことができ、処理精度を高めることができる。好ましい濃度は４０質量％以下であり、より好ましくは３０質量％以下である。なお図４の紫外線発光装置１ａを形成する場合、レンズ部の形成段階では、粘度の比較的高い塗布溶液にすることが好ましい。
The concentration of the resin composition in the coating liquid is, for example, 1% by mass or more. The higher the concentration, the less the number of coatings can be applied. The preferable concentration is 5% by mass or more, and more preferably 7% by mass or more. The concentration is, for example, 50% by mass or less. The lower the concentration, the more the viscosity of the coating liquid can be prevented from being improved, and the processing accuracy can be improved. The preferable concentration is 40% by mass or less, and more preferably 30% by mass or less. When forming the ultraviolet light emitting device 1a of FIG. 4, it is preferable to use a coating solution having a relatively high viscosity at the stage of forming the lens portion.
図３や図４の紫外線発光装置１、１ａの封止は、本発明の樹脂組成物を適当な温度に加熱して溶融し、溶融物を紫外線発光素子２上に流し込むことによっても製造できる。該加熱温度は、前記フッ素樹脂の融点以上であり、融点＋１０℃以上が好ましく、融点＋２０℃以上がより好ましい。加熱温度の上限は、例えば、２７０℃であり、より好ましくは２００℃であり、更により好ましくは１５０℃である。
The sealing of the ultraviolet light emitting devices 1 and 1a of FIGS. 3 and 4 can also be produced by heating the resin composition of the present invention to an appropriate temperature to melt it and pouring the melt onto the ultraviolet light emitting element 2. The heating temperature is equal to or higher than the melting point of the fluororesin, preferably melting point + 10 ° C. or higher, and more preferably melting point + 20 ° C. or higher. The upper limit of the heating temperature is, for example, 270 ° C, more preferably 200 ° C, and even more preferably 150 ° C.
また図３や図４の紫外線発光装置１、１ａの封止は、本発明の樹脂組成物をシート状に成形し、該シートを紫外線発光素子実装パッケージの紫外線発光素子実装側に積層した後、該シートを融点以上に加熱して溶融し、冷却することによっても行うこともできる（以下この封止方法を「溶融封止法」という場合がある）。
Further, in the sealing of the ultraviolet light emitting devices 1 and 1a of FIGS. 3 and 4, the resin composition of the present invention is molded into a sheet, and the sheet is laminated on the ultraviolet light emitting element mounting side of the ultraviolet light emitting element mounting package, and then. It can also be carried out by heating the sheet above its melting point to melt it and then cooling it (hereinafter, this sealing method may be referred to as a "melt sealing method").
溶融封止法を行う場合のシートの加熱温度は、前記フッ素樹脂の融点より１０℃以上高い温度が好ましく、融点より２０℃以上高い温度がより好ましい。加熱温度の上限は、例えば、２７８℃であり、より好ましくは２５０℃であり、更により好ましくは２００℃であり、特に好ましくは１５０℃である。上記の加熱温度であれば、熱による紫外線発光素子実装パッケージの劣化などを抑制することができる。
When the melt sealing method is performed, the heating temperature of the sheet is preferably 10 ° C. or higher higher than the melting point of the fluororesin, and more preferably 20 ° C. or higher higher than the melting point. The upper limit of the heating temperature is, for example, 278 ° C., more preferably 250 ° C., even more preferably 200 ° C., and particularly preferably 150 ° C. At the above heating temperature, deterioration of the ultraviolet light emitting element mounting package due to heat can be suppressed.
前記シートの加熱は、大気中などの酸素含有雰囲気下で行ってもよいが、窒素雰囲気中、アルゴン雰囲気中などの不活性ガス雰囲気下で行う方が好ましい。さらにフッ素樹脂の加熱は、大気圧下で行ってもよいが、真空中などの減圧下で行うことも好ましい。減圧下でフッ素樹脂を加熱すると、封止後の樹脂中に残存する気泡が低減されて透明性が向上する。
The sheet may be heated in an oxygen-containing atmosphere such as the atmosphere, but it is preferably performed in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere. Further, the fluororesin may be heated under atmospheric pressure, but it is also preferable to heat the fluororesin under reduced pressure such as in vacuum. When the fluororesin is heated under reduced pressure, the bubbles remaining in the resin after sealing are reduced and the transparency is improved.
なお、前記シートは、本発明のフッ素樹脂とフィラーが混合されたペレットを作製して、プレス、もしくは必要に応じて熱をかけながらプレスを行うことにより作製することができる。また、溶融状態のフッ素樹脂に無機フィラーを混合し、押出成形により作製することもできる。上記ペレットは、フッ素樹脂とフィラーの混合体を細かく切断することにより得ることができる。フッ素樹脂とフィラーの混合体は、熱により溶融状態になったフッ素樹脂にフィラーを混ぜ込む方法、及びフッ素樹脂を溶媒に溶解させて溶液とした後、フィラーを混合し、溶媒を乾燥させる方法、フッ素樹脂とフィラーと溶媒とを混合して、混合溶液にフッ素樹脂に対する貧溶媒を加え、フィラーを巻き込んだ状態でフッ素樹脂を析出させ、乾燥させる方法等により得ることができる。このうちフィラーを巻き込んだ状態でフッ素樹脂を析出させる方法が好ましい。
The sheet can be produced by producing pellets in which the fluororesin and the filler of the present invention are mixed and pressing, or if necessary, pressing while applying heat. Further, it can also be produced by mixing an inorganic filler with a molten fluororesin and extrusion molding. The pellet can be obtained by finely cutting a mixture of fluororesin and filler. For the mixture of fluororesin and filler, a method of mixing the filler with the fluororesin melted by heat, and a method of dissolving the fluororesin in a solvent to prepare a solution, then mixing the filler and drying the solvent. It can be obtained by a method of mixing a fluororesin, a filler and a solvent, adding a poor solvent to the fluororesin to the mixed solution, precipitating the fluororesin in a state where the filler is involved, and drying the fluororesin. Of these, a method of precipitating the fluororesin with the filler involved is preferable.
本発明の樹脂組成物を０．５ｍｍ厚のシートに形成した際の波長２６５ｎｍにおける光の透過率は、８％以上であることが好ましく、より好ましくは３０％以上、更に好ましくは４０％以上、特に好ましくは５０％以上であり、また波長３５０ｎｍにおける光の透過率は、２５％以上であることが好ましく、より好ましくは５０％以上、更に好ましくは６０％以上、特に好ましくは７０％以上であり、また波長５００ｎｍにおける光の透過率は、６０％以上であることが好ましく、より好ましくは７０％以上、更に好ましくは７５％以上、特に好ましくは８０％以上である。これにより封止部の透明性が向上し、紫外線発光素子からの光取出し効率を向上することができる。なお、光の透過率は高いほど好ましいが、波長２６５ｎｍにおける光の透過率は、例えば８０％以下であってもよく、波長３５０ｎｍにおける光の透過率は、例えば９０％以下であってもよく、波長５００ｎｍにおける光の透過率は、例えば９５％以下であってもよい。
When the resin composition of the present invention is formed on a sheet having a thickness of 0.5 mm, the light transmittance at a wavelength of 265 nm is preferably 8% or more, more preferably 30% or more, still more preferably 40% or more. Particularly preferably, it is 50% or more, and the transmittance of light at a wavelength of 350 nm is preferably 25% or more, more preferably 50% or more, still more preferably 60% or more, and particularly preferably 70% or more. The light transmittance at a wavelength of 500 nm is preferably 60% or more, more preferably 70% or more, still more preferably 75% or more, and particularly preferably 80% or more. As a result, the transparency of the sealing portion is improved, and the light extraction efficiency from the ultraviolet light emitting element can be improved. The higher the light transmittance is, the more preferable it is. However, the light transmittance at a wavelength of 265 nm may be, for example, 80% or less, and the light transmittance at a wavelength of 350 nm may be, for example, 90% or less. The transmittance of light at a wavelength of 500 nm may be, for example, 95% or less.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明は下記実施例によって制限されず、前・後記の趣旨に適合し得る範囲で変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples, and of course, it is possible to carry out the present invention with modifications to the extent that it can be adapted to the gist of the above and the following. And all of them are included in the technical scope of the present invention.
〈ＮＭＲ測定〉
フッ素樹脂であるスリーエムジャパン株式会社製のダイニオンＴＨＶ２２１ＡＺ粉末（以下ではＴＨＶ２２１ＡＺと呼ぶ）と、ダイキン工業株式会社製のＤＡＩ－ＥＬ Ｇ－５０１ＮＫ（以下ではＤＡＩ－ＥＬ Ｇ－５０１ＮＫと呼ぶ）のそれぞれについて、下記条件で構成単位Ａ、構成単位Ｂ、構成単位Ｃの各モル比を求めた。その結果を表１に示す。
測定装置：ＪＥＯＬ ＥＣＺ－４００
試料：約６０ｍｇ／０．８ｍｌ ＡＣＴ－ｄ６
ＩＳ：４－クロロベンゾドリフルオリド ０．０１ｍＬ
測定モード：1Ｈ、19Ｆ
緩和時間：1Ｈ ３０秒、19Ｆ ２０秒
構成単位Ｂのユニット数：ＣＦ3の積分比を３で除して算出（ＣＦ3積分比／３）
構成単位Ｃのユニット数：ＣＨ2の積分比を２で除して算出（ＣＨ2積分比／２）
構成単位Ａのユニット数：ＣＦ2の合計積分比より、構成単位Ｂ由来のＣＦ2と構成単位Ｃ由来のＣＦ2を差し引いたものを４で除して算出（（ＣＦ2合計積分比－構成単位Ｃのユニット数×２－構成単位Ｂのユニット数×２）／４） <NMR measurement>
Regarding each of the fluororesin Dynon THV221AZ powder manufactured by 3M Japan Ltd. (hereinafter referred to as THV221AZ) and DAI-EL G-501NK manufactured by Daikin Industries, Ltd. (hereinafter referred to as DAI-EL G-501NK). The molar ratios of the constituent unit A, the constituent unit B, and the constituent unit C were determined under the following conditions. The results are shown in Table 1.
Measuring device: JEOL ECZ-400
Sample: Approximately 60 mg / 0.8 ml ACT-d6
IS: 4-Chlorobenzodrifluoride 0.01 mL
Measurement mode: 1 H, 19 F
Relaxation time: 1 H 30 seconds, 19 F 20 seconds Number of units in building block B: Calculated by dividing the integration ratio of CF 3 by 3 (CF 3 integration ratio / 3)
Number of units in building block C: Calculated by dividing the integration ratio of CH 2 by 2 (CH 2 integration ratio / 2)
The number of units of the structural unit A: than the total area ratio of CF 2, calculated by dividing the minus the CF 2 constituent units derived from C and CF 2 derived from structural units B in 4 ((CF 2 Total integration ratio - structure Number of units in unit C x 2-Number of units in configuration unit B x 2) / 4)
フッ素樹脂であるスリーエムジャパン株式会社製のダイニオンＴＨＶ２２１ＡＺ粉末（以下ではＴＨＶ２２１ＡＺと呼ぶ）と、ダイキン工業株式会社製のＤＡＩ－ＥＬ Ｇ－５０１ＮＫ（以下ではＤＡＩ－ＥＬ Ｇ－５０１ＮＫと呼ぶ）のそれぞれについて、下記条件で構成単位Ａ、構成単位Ｂ、構成単位Ｃの各モル比を求めた。その結果を表１に示す。
測定装置：ＪＥＯＬ ＥＣＺ－４００
試料：約６０ｍｇ／０．８ｍｌ ＡＣＴ－ｄ６
ＩＳ：４－クロロベンゾドリフルオリド ０．０１ｍＬ
測定モード：1Ｈ、19Ｆ
緩和時間：1Ｈ ３０秒、19Ｆ ２０秒
構成単位Ｂのユニット数：ＣＦ3の積分比を３で除して算出（ＣＦ3積分比／３）
構成単位Ｃのユニット数：ＣＨ2の積分比を２で除して算出（ＣＨ2積分比／２）
構成単位Ａのユニット数：ＣＦ2の合計積分比より、構成単位Ｂ由来のＣＦ2と構成単位Ｃ由来のＣＦ2を差し引いたものを４で除して算出（（ＣＦ2合計積分比－構成単位Ｃのユニット数×２－構成単位Ｂのユニット数×２）／４） <NMR measurement>
Regarding each of the fluororesin Dynon THV221AZ powder manufactured by 3M Japan Ltd. (hereinafter referred to as THV221AZ) and DAI-EL G-501NK manufactured by Daikin Industries, Ltd. (hereinafter referred to as DAI-EL G-501NK). The molar ratios of the constituent unit A, the constituent unit B, and the constituent unit C were determined under the following conditions. The results are shown in Table 1.
Measuring device: JEOL ECZ-400
Sample: Approximately 60 mg / 0.8 ml ACT-d6
IS: 4-Chlorobenzodrifluoride 0.01 mL
Measurement mode: 1 H, 19 F
Relaxation time: 1 H 30 seconds, 19 F 20 seconds Number of units in building block B: Calculated by dividing the integration ratio of CF 3 by 3 (CF 3 integration ratio / 3)
Number of units in building block C: Calculated by dividing the integration ratio of CH 2 by 2 (CH 2 integration ratio / 2)
The number of units of the structural unit A: than the total area ratio of CF 2, calculated by dividing the minus the CF 2 constituent units derived from C and CF 2 derived from structural units B in 4 ((CF 2 Total integration ratio - structure Number of units in unit C x 2-Number of units in configuration unit B x 2) / 4)
〈密着性評価〉
フッ素樹脂の密着性は、以下の２種類のフッ素樹脂を使用して碁盤目試験を行うことで評価した。固化物の剥がれが全く無かったものを剥がれ「無」、固化物が全て剥がれたものを剥がれ「有」と評価した。評価結果を表２に示す。 <Adhesion evaluation>
The adhesion of the fluororesin was evaluated by performing a grid test using the following two types of fluororesins. Those with no peeling of the solidified material were evaluated as "none", and those with all the solidified material peeled off were evaluated as "presence". The evaluation results are shown in Table 2.
フッ素樹脂の密着性は、以下の２種類のフッ素樹脂を使用して碁盤目試験を行うことで評価した。固化物の剥がれが全く無かったものを剥がれ「無」、固化物が全て剥がれたものを剥がれ「有」と評価した。評価結果を表２に示す。 <Adhesion evaluation>
The adhesion of the fluororesin was evaluated by performing a grid test using the following two types of fluororesins. Those with no peeling of the solidified material were evaluated as "none", and those with all the solidified material peeled off were evaluated as "presence". The evaluation results are shown in Table 2.
（１）無機フィラーを含まないフッ素樹脂（樹脂組成物１、２）
まずＡｌ基板上に耐熱テープ（厚み０．１９ｍｍ、ガラスクロステープ）でダムを作り縦３．５ｃｍ×横４．０ｃｍの領域を複数作製した。更にフッ素樹脂であるＴＨＶ２２１ＡＺとＤＡＩ－ＥＬ Ｇ－５０１ＮＫのそれぞれを酢酸プロピルに添加して、濃度が９質量％の酢酸プロピル溶液を調製して樹脂組成物１、樹脂組成物２を得た。次いで、樹脂組成物１、樹脂組成物２をそれぞれ４００μｌずつ異なる上記領域に入れた後、２００℃、３時間、加熱して、冷却することによりフッ素樹脂が固化した固化物をそれぞれ得た。得られた固化物に対して、カッターとカッタガイドを用いて切込を入れて、それぞれ１ｍｍ角の基盤目を１００個作り、基盤目を全て覆うようにスコッチ（登録商標）メンディングテープ（３Ｍ社製の「８１０－３－１８」）を貼り付けた。その後、Ａｌ基板に対して上方向にスコッチテープを剥がし、固化物の剥がれの有無をデジタルマイクロスコープ（２０倍）で観察した。 (1) Fluororesin containing no inorganic filler (resin compositions 1 and 2)
First, a dam was formed on an Al substrate with a heat-resistant tape (thickness 0.19 mm, glass cloth tape) to prepare a plurality of regions having a length of 3.5 cm and a width of 4.0 cm. Further, each of the fluororesins THV221AZ and DAI-EL G-501NK was added to propyl acetate to prepare a propyl acetate solution having a concentration of 9% by mass to obtain aresin composition 1 and a resin composition 2. Next, the resin composition 1 and the resin composition 2 were placed in different regions by 400 μl each, and then heated and cooled at 200 ° C. for 3 hours to obtain a solidified product in which the fluororesin was solidified. Use a cutter and a cutter guide to make cuts in the obtained solidified product to make 100 1 mm square base stitches, and scotch (registered trademark) mending tape (3M) so as to cover all the base stitches. The company's "810-3-18") was pasted. Then, the scotch tape was peeled upward with respect to the Al substrate, and the presence or absence of peeling of the solidified material was observed with a digital microscope (20 times).
まずＡｌ基板上に耐熱テープ（厚み０．１９ｍｍ、ガラスクロステープ）でダムを作り縦３．５ｃｍ×横４．０ｃｍの領域を複数作製した。更にフッ素樹脂であるＴＨＶ２２１ＡＺとＤＡＩ－ＥＬ Ｇ－５０１ＮＫのそれぞれを酢酸プロピルに添加して、濃度が９質量％の酢酸プロピル溶液を調製して樹脂組成物１、樹脂組成物２を得た。次いで、樹脂組成物１、樹脂組成物２をそれぞれ４００μｌずつ異なる上記領域に入れた後、２００℃、３時間、加熱して、冷却することによりフッ素樹脂が固化した固化物をそれぞれ得た。得られた固化物に対して、カッターとカッタガイドを用いて切込を入れて、それぞれ１ｍｍ角の基盤目を１００個作り、基盤目を全て覆うようにスコッチ（登録商標）メンディングテープ（３Ｍ社製の「８１０－３－１８」）を貼り付けた。その後、Ａｌ基板に対して上方向にスコッチテープを剥がし、固化物の剥がれの有無をデジタルマイクロスコープ（２０倍）で観察した。 (1) Fluororesin containing no inorganic filler (
First, a dam was formed on an Al substrate with a heat-resistant tape (thickness 0.19 mm, glass cloth tape) to prepare a plurality of regions having a length of 3.5 cm and a width of 4.0 cm. Further, each of the fluororesins THV221AZ and DAI-EL G-501NK was added to propyl acetate to prepare a propyl acetate solution having a concentration of 9% by mass to obtain a
（２）無機フィラーを含むフッ素樹脂（樹脂組成物３、４）
上記（１）と同様にして、ＴＨＶ２２１ＡＺとＤＡＩ－ＥＬ Ｇ－５０１ＮＫのそれぞれを酢酸プロピルに添加して、濃度が９質量％の酢酸プロピル溶液を調製した。その後、それぞれの溶液１０ｇに対して、後述する粒径が１１μｍのＭｇＦ2粉末（２）を０．３６ｇ混合し、自転公転ミキサー（あわとり練太郎ＡＲＶ－３１０、株式会社シンキー社製）で、２００ｒｐｍで３分間混合する操作を２回行って、樹脂溶液中にフィラーが分散した溶液、即ち樹脂組成物３、樹脂組成物４を得た。この樹脂組成物３、樹脂組成物４を使用したこと以外は、上記（１）と同様にして評価を行った。 (2) Fluororesin containing an inorganic filler (resin compositions 3, 4)
In the same manner as in (1) above, THV221AZ and DAI-EL G-501NK were each added to propyl acetate to prepare a propyl acetate solution having a concentration of 9% by mass. Then, 0.36 g of MgF 2 powder (2) having a particle size of 11 μm, which will be described later, is mixed with 10 g of each solution, and a rotating revolution mixer (Awatori Rentaro ARV-310, manufactured by Shinky Co., Ltd.) is used. The operation of mixing at 200 rpm for 3 minutes was performed twice to obtain a solution in which the filler was dispersed in the resin solution, that is, the resin composition 3 and theresin composition 4. The evaluation was carried out in the same manner as in (1) above, except that the resin composition 3 and the resin composition 4 were used.
上記（１）と同様にして、ＴＨＶ２２１ＡＺとＤＡＩ－ＥＬ Ｇ－５０１ＮＫのそれぞれを酢酸プロピルに添加して、濃度が９質量％の酢酸プロピル溶液を調製した。その後、それぞれの溶液１０ｇに対して、後述する粒径が１１μｍのＭｇＦ2粉末（２）を０．３６ｇ混合し、自転公転ミキサー（あわとり練太郎ＡＲＶ－３１０、株式会社シンキー社製）で、２００ｒｐｍで３分間混合する操作を２回行って、樹脂溶液中にフィラーが分散した溶液、即ち樹脂組成物３、樹脂組成物４を得た。この樹脂組成物３、樹脂組成物４を使用したこと以外は、上記（１）と同様にして評価を行った。 (2) Fluororesin containing an inorganic filler (resin compositions 3, 4)
In the same manner as in (1) above, THV221AZ and DAI-EL G-501NK were each added to propyl acetate to prepare a propyl acetate solution having a concentration of 9% by mass. Then, 0.36 g of MgF 2 powder (2) having a particle size of 11 μm, which will be described later, is mixed with 10 g of each solution, and a rotating revolution mixer (Awatori Rentaro ARV-310, manufactured by Shinky Co., Ltd.) is used. The operation of mixing at 200 rpm for 3 minutes was performed twice to obtain a solution in which the filler was dispersed in the resin solution, that is, the resin composition 3 and the
表１、２に示す通り、構成単位Ａのモル比（Ａ）が０．２５以上であり、且つ構成単位Ｃのモル比（Ｃ）が０．６０以下であるＴＨＶ２２１ＡＺを含有する樹脂組成物１、３の固化物は、優れた密着性を示した。一方、構成単位Ａのモル比（Ａ）が０．２５未満であり、且つ構成単位Ｃのモル比（Ｃ）が０．６０超であるＤＡＩ－ＥＬ Ｇ－５０１ＮＫを含有する樹脂組成物２、４の固化物は、密着性に劣っていた。
As shown in Tables 1 and 2, the resin composition 1 containing THV221AZ in which the molar ratio (A) of the constituent unit A is 0.25 or more and the molar ratio (C) of the constituent unit C is 0.60 or less. The solidified product of No. 3 showed excellent adhesion. On the other hand, the resin composition 2 containing DAI-EL G-501NK in which the molar ratio (A) of the constituent unit A is less than 0.25 and the molar ratio (C) of the constituent unit C is more than 0.60. The solidified product of No. 4 was inferior in adhesion.
以下の実施例では、無機フィラーとして以下のＭｇＦ2粉末（１）～（３）のいずれかを使用した。
＜ＭｇＦ2粉末（１）（Ｄ50＝２１８μｍ）＞
ピアーオプティックス株式会社製のＭｇＦ2粉末（品番：ＭＦＧＲ３－６を粉砕し、６０メッシュの篩を通過したもの、Ｄ50＝２１８μｍ）を粉砕せずに使用した。
＜ＭｇＦ2粉末（２）（Ｄ50＝１１μｍ）＞
ピアーオプティックス株式会社製のＭｇＦ2粉末（Ｄ50＝２１８μｍ）を、以下の条件にてボールミルで粉砕することにより、ＭｇＦ2粉末の粒度を調節して、Ｄ50＝１１μｍ、ＢＥＴ法により測定した比表面積が１．４ｍ2／ｇのＭｇＦ2粉末（２）を得た。
粉砕条件
粉砕装置：ボールミルＡＮＺ－５１Ｓ（日陶科学株式会社製）
容器：２５０ｍｌアイボーイ（アズワン株式会社製 品番５－００２－０３）
メディア：４００ｇ ジルコニアボール ５ｍｍφ（アズワン株式会社製 品番：２－９１９１－１６）
ＭｇＦ2粉末：６０ｇ
溶媒：イソプロピルアルコール（ナカライテクス株式会社製） １００ｇ
回転数：１２６ｒｐｍ
粉砕時間：４時間
＜ＭｇＦ2粉末（３）（Ｄ50＝１７μｍ）＞
日清エンジニアリング株式会社製のＭｇＦ2粉末（Ｄ50＝１７μｍ、ＢＥＴ法により測定した比表面積が４３ｍ2／ｇ）を粉砕せずに使用した。 In the following examples, any of the following MgF 2 powders (1) to (3) was used as the inorganic filler.
<MgF 2 powder (1) (D 50 = 218 μm)>
MgF 2 powder manufactured by Pear Optics Co., Ltd. (product number: MFGR3-6 crushed and passed through a 60 mesh sieve, D 50 = 218 μm) was used without crushing.
<MgF 2 powder (2) (D 50 = 11 μm)>
MgF 2 powder (D 50 = 218 μm) manufactured by Pear Optics Co., Ltd. was pulverized with a ball mill under the following conditions to adjust the particle size of MgF 2 powder, and measured by the BET method at D 50 = 11 μm. MgF 2 powder (2) having a specific surface area of 1.4 m 2 / g was obtained.
Crushing conditions Crushing device: Ball mill ANZ-51S (manufactured by Nikko Kagaku Co., Ltd.)
Container: 250 ml Iboy (manufactured by AS ONE Corporation, product number 5-002-03)
Media: 400g Zirconia ball 5mmφ (Manufactured by AS ONE Corporation Part number: 2-9191-1-16)
MgF 2 powder: 60 g
Solvent: Isopropyl alcohol (manufactured by Nacalai Tesque, Inc.) 100 g
Rotation speed: 126 rpm
Grinding time: 4 hours <MgF 2 powder (3) (D 50 = 17 μm)>
MgF 2 powder (D 50 = 17 μm, specific surface area measured by BET method: 43 m 2 / g) manufactured by Nisshin Engineering Co., Ltd. was used without pulverization.
＜ＭｇＦ2粉末（１）（Ｄ50＝２１８μｍ）＞
ピアーオプティックス株式会社製のＭｇＦ2粉末（品番：ＭＦＧＲ３－６を粉砕し、６０メッシュの篩を通過したもの、Ｄ50＝２１８μｍ）を粉砕せずに使用した。
＜ＭｇＦ2粉末（２）（Ｄ50＝１１μｍ）＞
ピアーオプティックス株式会社製のＭｇＦ2粉末（Ｄ50＝２１８μｍ）を、以下の条件にてボールミルで粉砕することにより、ＭｇＦ2粉末の粒度を調節して、Ｄ50＝１１μｍ、ＢＥＴ法により測定した比表面積が１．４ｍ2／ｇのＭｇＦ2粉末（２）を得た。
粉砕条件
粉砕装置：ボールミルＡＮＺ－５１Ｓ（日陶科学株式会社製）
容器：２５０ｍｌアイボーイ（アズワン株式会社製 品番５－００２－０３）
メディア：４００ｇ ジルコニアボール ５ｍｍφ（アズワン株式会社製 品番：２－９１９１－１６）
ＭｇＦ2粉末：６０ｇ
溶媒：イソプロピルアルコール（ナカライテクス株式会社製） １００ｇ
回転数：１２６ｒｐｍ
粉砕時間：４時間
＜ＭｇＦ2粉末（３）（Ｄ50＝１７μｍ）＞
日清エンジニアリング株式会社製のＭｇＦ2粉末（Ｄ50＝１７μｍ、ＢＥＴ法により測定した比表面積が４３ｍ2／ｇ）を粉砕せずに使用した。 In the following examples, any of the following MgF 2 powders (1) to (3) was used as the inorganic filler.
<MgF 2 powder (1) (D 50 = 218 μm)>
MgF 2 powder manufactured by Pear Optics Co., Ltd. (product number: MFGR3-6 crushed and passed through a 60 mesh sieve, D 50 = 218 μm) was used without crushing.
<MgF 2 powder (2) (D 50 = 11 μm)>
MgF 2 powder (D 50 = 218 μm) manufactured by Pear Optics Co., Ltd. was pulverized with a ball mill under the following conditions to adjust the particle size of MgF 2 powder, and measured by the BET method at D 50 = 11 μm. MgF 2 powder (2) having a specific surface area of 1.4 m 2 / g was obtained.
Crushing conditions Crushing device: Ball mill ANZ-51S (manufactured by Nikko Kagaku Co., Ltd.)
Container: 250 ml Iboy (manufactured by AS ONE Corporation, product number 5-002-03)
Media: 400g Zirconia ball 5mmφ (Manufactured by AS ONE Corporation Part number: 2-9191-1-16)
MgF 2 powder: 60 g
Solvent: Isopropyl alcohol (manufactured by Nacalai Tesque, Inc.) 100 g
Rotation speed: 126 rpm
Grinding time: 4 hours <MgF 2 powder (3) (D 50 = 17 μm)>
MgF 2 powder (D 50 = 17 μm, specific surface area measured by BET method: 43 m 2 / g) manufactured by Nisshin Engineering Co., Ltd. was used without pulverization.
〈ＭｇＦ2粉末の粒度分布測定〉
無機フィラーの粒度分布測定は、下記条件のレーザー回折法により、各調製済のＭｇＦ2粉末の粒度の積算分布曲線を得て、体積累積頻度５０％における粒径である粒径Ｄ50を求める方法で行った。
測定装置：ＳＡＬＤ－２０００Ｊ （株式会社島津製作所製）
分散溶媒：イオン交換水＋中性洗剤
分散方法：スターラー撹拌＋超音波照射 １０分
屈折率（ＭｇＦ2）：１．４０－０．２０ｉ <Measurement of particle size distribution of MgF 2 powder>
The particle size distribution of the inorganic filler is measured by obtaining an integrated distribution curve of the particle size of each prepared MgF 2 powder by a laser diffraction method under the following conditions, and obtaining the particle size D 50 , which is the particle size at a volume cumulative frequency of 50%. I went there.
Measuring device: SALD-2000J (manufactured by Shimadzu Corporation)
Dispersion solvent: Ion-exchanged water + Neutral detergent Dispersion method: Stirrer stirring +Ultrasonic irradiation 10 minutes Refractive index (MgF 2 ): 1.40-0.20i
無機フィラーの粒度分布測定は、下記条件のレーザー回折法により、各調製済のＭｇＦ2粉末の粒度の積算分布曲線を得て、体積累積頻度５０％における粒径である粒径Ｄ50を求める方法で行った。
測定装置：ＳＡＬＤ－２０００Ｊ （株式会社島津製作所製）
分散溶媒：イオン交換水＋中性洗剤
分散方法：スターラー撹拌＋超音波照射 １０分
屈折率（ＭｇＦ2）：１．４０－０．２０ｉ <Measurement of particle size distribution of MgF 2 powder>
The particle size distribution of the inorganic filler is measured by obtaining an integrated distribution curve of the particle size of each prepared MgF 2 powder by a laser diffraction method under the following conditions, and obtaining the particle size D 50 , which is the particle size at a volume cumulative frequency of 50%. I went there.
Measuring device: SALD-2000J (manufactured by Shimadzu Corporation)
Dispersion solvent: Ion-exchanged water + Neutral detergent Dispersion method: Stirrer stirring +
〈屈折率測定〉
ジェー・エー・ウーラム・ジャパン株式会社製の高速分光エリプソメーター（Ｍ－２０００）を用いて、ＴＨＶ２２１ＡＺ、及びＭｇＦ2粉末（１）の波長５８９ｎｍの光に対する屈折率を測定したところ、それぞれ１．３６、１．３８であった。なおＭｇＦ2粉末（２）の屈折率は測定していないが、上記程度の粉砕条件では屈折率はほとんど変化しないため、ＭｇＦ2粉末（２）はＭｇＦ2粉末（１）と同等の屈折率を示すと考えられる。 <Measurement of refractive index>
The refractive indexes of THV221AZ and MgF 2 powder (1) with respect to light at a wavelength of 589 nm were measured using a high-speed spectroscopic ellipsometer (M-2000) manufactured by JA Woolam Japan Co., Ltd. , 1.38. Note refractive index of MgF 2 powder (2) is not measured, because hardly changes the refractive index in the grinding condition of about the, MgF 2 powder (2) is the same refractive index as MgF 2 powder (1) It is thought to show.
ジェー・エー・ウーラム・ジャパン株式会社製の高速分光エリプソメーター（Ｍ－２０００）を用いて、ＴＨＶ２２１ＡＺ、及びＭｇＦ2粉末（１）の波長５８９ｎｍの光に対する屈折率を測定したところ、それぞれ１．３６、１．３８であった。なおＭｇＦ2粉末（２）の屈折率は測定していないが、上記程度の粉砕条件では屈折率はほとんど変化しないため、ＭｇＦ2粉末（２）はＭｇＦ2粉末（１）と同等の屈折率を示すと考えられる。 <Measurement of refractive index>
The refractive indexes of THV221AZ and MgF 2 powder (1) with respect to light at a wavelength of 589 nm were measured using a high-speed spectroscopic ellipsometer (M-2000) manufactured by JA Woolam Japan Co., Ltd. , 1.38. Note refractive index of MgF 2 powder (2) is not measured, because hardly changes the refractive index in the grinding condition of about the, MgF 2 powder (2) is the same refractive index as MgF 2 powder (1) It is thought to show.
〈比表面積測定〉
前処理として、１５０℃で３０分の処理条件で無機フィラーを加熱処理し、測定試料を調製した。かかる測定試料について、ＢＥＴ法により比表面積を算出した。
測定装置：ＭＯＮＯＳＯＲＢ（ユアサ アイオニクス株式会社製）
吸着質：Ｎ2 <Specific surface area measurement>
As a pretreatment, the inorganic filler was heat-treated at 150 ° C. for 30 minutes to prepare a measurement sample. The specific surface area of such a measurement sample was calculated by the BET method.
Measuring device: MONOSORB (manufactured by Yuasa Ionics Co., Ltd.)
Adsorbent: N 2
前処理として、１５０℃で３０分の処理条件で無機フィラーを加熱処理し、測定試料を調製した。かかる測定試料について、ＢＥＴ法により比表面積を算出した。
測定装置：ＭＯＮＯＳＯＲＢ（ユアサ アイオニクス株式会社製）
吸着質：Ｎ2 <Specific surface area measurement>
As a pretreatment, the inorganic filler was heat-treated at 150 ° C. for 30 minutes to prepare a measurement sample. The specific surface area of such a measurement sample was calculated by the BET method.
Measuring device: MONOSORB (manufactured by Yuasa Ionics Co., Ltd.)
Adsorbent: N 2
〈樹脂組成物の固化物の調製〉
実施例１
０．２０ｇのＴＨＶ２２１ＡＺを石英ガラス板上に乗せて、２００℃のホットプレート上で加熱融解させた。その上にＭｇＦ2粉末（３）を０．０８ｇ添加し、ヘラ状のスパチュラ２本を用いて混合し、冷却して樹脂組成物の固化物を得た。 <Preparation of solidified resin composition>
Example 1
0.20 g of THV221AZ was placed on a quartz glass plate and melted by heating on a hot plate at 200 ° C. 0.08 g of MgF 2 powder (3) was added thereto, mixed using two spatula-shaped spatulas, and cooled to obtain a solidified resin composition.
実施例１
０．２０ｇのＴＨＶ２２１ＡＺを石英ガラス板上に乗せて、２００℃のホットプレート上で加熱融解させた。その上にＭｇＦ2粉末（３）を０．０８ｇ添加し、ヘラ状のスパチュラ２本を用いて混合し、冷却して樹脂組成物の固化物を得た。 <Preparation of solidified resin composition>
Example 1
0.20 g of THV221AZ was placed on a quartz glass plate and melted by heating on a hot plate at 200 ° C. 0.08 g of MgF 2 powder (3) was added thereto, mixed using two spatula-shaped spatulas, and cooled to obtain a solidified resin composition.
実施例２
ＴＨＶ２２１ＡＺの含量が２０質量％となるように、ＴＨＶ２２１ＡＺを酢酸ブチルに添加し、溶解させた。得られた混合溶液をスクリュー管に８．０ｇ秤とり、撹拌子で攪拌しながらＭｇＦ2粉末（２）を０．２９ｇ添加して均一の混合溶液とした。次いで、貧溶媒であるエタノール２０ｇを入れてフィラーを含有したフッ素樹脂を析出させた。析出した樹脂をスクリュー管から取り出し、８０℃、５時間の条件で乾燥させて樹脂組成物の固化物を得た。 Example 2
THV221AZ was added to butyl acetate and dissolved so that the content of THV221AZ was 20% by mass. 8.0 g of the obtained mixed solution was weighed into a screw tube, and 0.29 g of MgF 2 powder (2) was added while stirring with a stirrer to obtain a uniform mixed solution. Next, 20 g of ethanol, which is a poor solvent, was added to precipitate a fluororesin containing a filler. The precipitated resin was taken out from the screw tube and dried at 80 ° C. for 5 hours to obtain a solidified resin composition.
ＴＨＶ２２１ＡＺの含量が２０質量％となるように、ＴＨＶ２２１ＡＺを酢酸ブチルに添加し、溶解させた。得られた混合溶液をスクリュー管に８．０ｇ秤とり、撹拌子で攪拌しながらＭｇＦ2粉末（２）を０．２９ｇ添加して均一の混合溶液とした。次いで、貧溶媒であるエタノール２０ｇを入れてフィラーを含有したフッ素樹脂を析出させた。析出した樹脂をスクリュー管から取り出し、８０℃、５時間の条件で乾燥させて樹脂組成物の固化物を得た。 Example 2
THV221AZ was added to butyl acetate and dissolved so that the content of THV221AZ was 20% by mass. 8.0 g of the obtained mixed solution was weighed into a screw tube, and 0.29 g of MgF 2 powder (2) was added while stirring with a stirrer to obtain a uniform mixed solution. Next, 20 g of ethanol, which is a poor solvent, was added to precipitate a fluororesin containing a filler. The precipitated resin was taken out from the screw tube and dried at 80 ° C. for 5 hours to obtain a solidified resin composition.
実施例３
添加したＭｇＦ2粉末（２）の量を０．６５ｇに変更したこと以外は実施例２と同様にして樹脂組成物の固化物を得た。 Example 3
A solidified resin composition was obtained in the same manner as in Example 2 except that the amount of the added MgF 2 powder (2) was changed to 0.65 g.
添加したＭｇＦ2粉末（２）の量を０．６５ｇに変更したこと以外は実施例２と同様にして樹脂組成物の固化物を得た。 Example 3
A solidified resin composition was obtained in the same manner as in Example 2 except that the amount of the added MgF 2 powder (2) was changed to 0.65 g.
実施例４
ＴＨＶ２２１ＡＺとＭｇＦ2粉末（２）を下記の条件で混錬して樹脂組成物の固化物を得た。
混錬装置：ラボプラストミル ３Ｓ１５０（株式会社東洋精機製作所製）
ミキサー：ローラミキサ Ｒ６０
設定温度：１４０℃
回転数：５０ｒｐｍ
混錬時間：５分
サンプル量：１００ｇ（ＴＨＶ２２１ＡＺ：７１．２ｇ、ＭｇＦ2粉末：２８．８ｇ） Example 4
THV221AZ and MgF 2 powder (2) were kneaded under the following conditions to obtain a solidified resin composition.
Kneading device: Labplast Mill 3S150 (manufactured by Toyo Seiki Seisakusho Co., Ltd.)
Mixer: Roller mixer R60
Set temperature: 140 ° C
Rotation speed: 50 rpm
Kneading time: 5 minutes Sample amount: 100 g (THV221AZ: 71.2 g, MgF 2 powder: 28.8 g)
ＴＨＶ２２１ＡＺとＭｇＦ2粉末（２）を下記の条件で混錬して樹脂組成物の固化物を得た。
混錬装置：ラボプラストミル ３Ｓ１５０（株式会社東洋精機製作所製）
ミキサー：ローラミキサ Ｒ６０
設定温度：１４０℃
回転数：５０ｒｐｍ
混錬時間：５分
サンプル量：１００ｇ（ＴＨＶ２２１ＡＺ：７１．２ｇ、ＭｇＦ2粉末：２８．８ｇ） Example 4
THV221AZ and MgF 2 powder (2) were kneaded under the following conditions to obtain a solidified resin composition.
Kneading device: Labplast Mill 3S150 (manufactured by Toyo Seiki Seisakusho Co., Ltd.)
Mixer: Roller mixer R60
Set temperature: 140 ° C
Rotation speed: 50 rpm
Kneading time: 5 minutes Sample amount: 100 g (THV221AZ: 71.2 g, MgF 2 powder: 28.8 g)
実施例５
添加したＭｇＦ2粉末（２）の量を１．１１ｇに変更したこと以外は実施例２と同様にして樹脂組成物の固化物を得た。 Example 5
A solidified resin composition was obtained in the same manner as in Example 2 except that the amount of the added MgF 2 powder (2) was changed to 1.11 g.
添加したＭｇＦ2粉末（２）の量を１．１１ｇに変更したこと以外は実施例２と同様にして樹脂組成物の固化物を得た。 Example 5
A solidified resin composition was obtained in the same manner as in Example 2 except that the amount of the added MgF 2 powder (2) was changed to 1.11 g.
実施例６
ＭｇＦ2粉末（１）を用いたこと、及び添加したＭｇＦ2粉末（１）の量を１．１１ｇとした以外は実施例２と同様にして樹脂組成物の固化物を得た。 Example 6
A solidified resin composition was obtained in the same manner as in Example 2 except that the MgF 2 powder (1) was used and the amount of the added MgF 2 powder (1) was 1.11 g.
ＭｇＦ2粉末（１）を用いたこと、及び添加したＭｇＦ2粉末（１）の量を１．１１ｇとした以外は実施例２と同様にして樹脂組成物の固化物を得た。 Example 6
A solidified resin composition was obtained in the same manner as in Example 2 except that the MgF 2 powder (1) was used and the amount of the added MgF 2 powder (1) was 1.11 g.
比較例１
ＴＨＶ２２１ＡＺをそのまま測定した。 Comparative Example 1
THV221AZ was measured as it was.
ＴＨＶ２２１ＡＺをそのまま測定した。 Comparative Example 1
THV221AZ was measured as it was.
〈耐熱性評価〉
実施例１～６で得られた樹脂組成物、及び比較例１のＴＨＶ２２１ＡＺの固化物の耐熱性を評価するために、下記条件で熱重量測定（ＴＧ測定）を行って、フッ素樹脂自体の質量が１０質量％低減したときの温度（１０％質量変化温度）を測定した。例えば樹脂組成物の固化物におけるフッ素樹脂の質量が７１.２質量％の場合には、フッ素樹脂が７．１２質量％減少したときの温度を測定した。また、データサンプリング間にフッ素樹脂自体の質量が１０質量％以上低減した場合は、１０質量％低減した直後のサンプリングの温度を１０％質量変化温度とした。実施例１～６、比較例１の耐熱性評価の結果を表３に示す。
測定装置：ＴＧ／ＤＴＡ６２００（エスアイアイ・ナノテクノロジー株式会社製）
測定雰囲気：大気
昇温範囲：３０℃から５００℃
昇温速度：１０℃／分
サンプリング間隔：４秒 <Heat resistance evaluation>
In order to evaluate the heat resistance of the resin compositions obtained in Examples 1 to 6 and the solidified product of THV221AZ of Comparative Example 1, thermal weight measurement (TG measurement) was performed under the following conditions, and the mass of the fluororesin itself was measured. The temperature (10% mass change temperature) when was reduced by 10% by mass was measured. For example, when the mass of the fluororesin in the solidified resin composition was 71.2% by mass, the temperature when the fluororesin was reduced by 7.12% by mass was measured. When the mass of the fluororesin itself was reduced by 10% by mass or more during data sampling, the sampling temperature immediately after the reduction by 10% by mass was defined as the 10% mass change temperature. Table 3 shows the results of heat resistance evaluation of Examples 1 to 6 and Comparative Example 1.
Measuring device: TG / DTA6200 (manufactured by SII Nanotechnology Co., Ltd.)
Measurement atmosphere: Atmosphere Temperature range: 30 ° C to 500 ° C
Temperature rise rate: 10 ° C / min Sampling interval: 4 seconds
実施例１～６で得られた樹脂組成物、及び比較例１のＴＨＶ２２１ＡＺの固化物の耐熱性を評価するために、下記条件で熱重量測定（ＴＧ測定）を行って、フッ素樹脂自体の質量が１０質量％低減したときの温度（１０％質量変化温度）を測定した。例えば樹脂組成物の固化物におけるフッ素樹脂の質量が７１.２質量％の場合には、フッ素樹脂が７．１２質量％減少したときの温度を測定した。また、データサンプリング間にフッ素樹脂自体の質量が１０質量％以上低減した場合は、１０質量％低減した直後のサンプリングの温度を１０％質量変化温度とした。実施例１～６、比較例１の耐熱性評価の結果を表３に示す。
測定装置：ＴＧ／ＤＴＡ６２００（エスアイアイ・ナノテクノロジー株式会社製）
測定雰囲気：大気
昇温範囲：３０℃から５００℃
昇温速度：１０℃／分
サンプリング間隔：４秒 <Heat resistance evaluation>
In order to evaluate the heat resistance of the resin compositions obtained in Examples 1 to 6 and the solidified product of THV221AZ of Comparative Example 1, thermal weight measurement (TG measurement) was performed under the following conditions, and the mass of the fluororesin itself was measured. The temperature (10% mass change temperature) when was reduced by 10% by mass was measured. For example, when the mass of the fluororesin in the solidified resin composition was 71.2% by mass, the temperature when the fluororesin was reduced by 7.12% by mass was measured. When the mass of the fluororesin itself was reduced by 10% by mass or more during data sampling, the sampling temperature immediately after the reduction by 10% by mass was defined as the 10% mass change temperature. Table 3 shows the results of heat resistance evaluation of Examples 1 to 6 and Comparative Example 1.
Measuring device: TG / DTA6200 (manufactured by SII Nanotechnology Co., Ltd.)
Measurement atmosphere: Atmosphere Temperature range: 30 ° C to 500 ° C
Temperature rise rate: 10 ° C / min Sampling interval: 4 seconds
〈透明性評価〉
下記に記載の方法でシートを作製し、透過率を測定した。
実施例７
ウォーターバスに置いたセパラブルフラスコに、酢酸ブチル（富士フイルム和光純薬株式会社製）１６０ｇを測り入れ、攪拌しながら、ウォーターバスを８５℃まで昇温した。攪拌しながら、ＴＨＶ２２１ＡＺを少しずつ４０ｇ加えて溶解させ、樹脂溶液を作製した。得られた溶液を１２０℃、３時間加熱し、残分から固形分濃度を求めたところ２０．２質量％であった。
上記で作製した２０．２質量％の濃度の樹脂溶液を１５ｇ、２５０ｍｌのディスポカップに入れ、そこにフィラーとしてＭｇＦ2粉末（２）を１．２２ｇ添加した。フィラーの濃度は、樹脂の密度を１．９５ｇ／ｃｍ3、ＭｇＦ2粉末の密度を３．１５ｇ／ｃｍ3として計算すると、２０体積％である。この溶液を、あわとり練太郎ＡＲＶ－３１０を用いて、回転数２０００ｒｐｍで２分間混合する操作を３回実施して、溶液とフィラーとを混合し、そこにマグネットスターラーを入れて攪拌してフィラーが均一に溶液中に舞っている状態を維持しながら、イソプロピルアルコール（ＩＰＡ、ナカライテクス株式会社製）７０ｇを一気に入れたところ、フィラーと一部の溶媒を巻き込みながら、樹脂が一気にゲル化して析出した。
ゲル化した塊状の試料を取り出し、該試料からスターラーを取り出した後、アルミカップの上に置いて、常温で乾燥させた。４時間程度乾燥させたところで、乾燥を促進させるためにハサミを用いておおよそ３ｃｍ角ぐらいのサイズに切り、その後、一晩乾燥させた。試料をハサミで５ｍｍ角程度に切り、１００℃に設定したホットプレートの上で３時間乾燥させた。
その後、試料をＰＦＡ製のシャーレに移し、真空乾燥機中で２００℃で３時間、脱泡、および乾燥させた。乾燥中は、試料は溶融しており、乾燥後はひと塊になっていた。得られた塊状の試料を再度、ハサミを用いて、２ｍｍ角程度のサイズに切り、ペレットとした。使用した樹脂とフィラーの合計量に対する収率は１００％であった。
厚さ５ｍｍ、１５ｃｍ角のＳＵＳ板の上に厚さ０．１ｍｍ、１５ｃｍ角のポリテトラフルオロエチレン（ＰＴＦＥ）フィルムを積層し、ＰＴＦＥフィルムの上に、中心に３ｃｍ角の貫通孔を備える厚さ０．５ｍｍ、１５ｃｍ角のＳＵＳ板を積層した。次いで上記ペレットを、上記３ｃｍ角の貫通孔の中に１．２ｇ入れた。更に厚さ０．１ｍｍ、１５ｃｍ角のＰＴＦＥフィルムと、厚さ５ｍｍ、１５ｃｍ角のＳＵＳ板とを順に積層して金型を組立てた。次いで、プレス機の温度を２００℃に設定し、加圧せずにプレス機の上下板を金型の上下の上記ＳＵＳ板に接触させた状態で３分保持してペレットを溶融させた。その後５０ＭＰａの圧力で２分間加圧した。加圧後に金型を取り出して、別途、水を通した２枚のＳＵＳ板で金型を挟んで十分に冷却して、金型を分解して、０．５ｍｍ厚みのフィラー含有フッ素樹脂シートを得、２６５ｎｍ、３５０ｎｍ、及び５００ｎｍにおける透過率を下記の条件に基づいて測定した。結果を表４に示す。
測定条件
測定装置：紫外可視近赤外分光光度計ＵＶ－３６００（株式会社島津製作所製）
アタッチメント：積分球 ＩＳＲ－３１００
バックグラウンド測定：大気 <Transparency evaluation>
A sheet was prepared by the method described below, and the transmittance was measured.
Example 7
160 g of butyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was weighed into a separable flask placed in a water bath, and the temperature of the water bath was raised to 85 ° C. with stirring. While stirring, 40 g of THV221AZ was gradually added and dissolved to prepare a resin solution. The obtained solution was heated at 120 ° C. for 3 hours, and the solid content concentration was determined from the residue and found to be 20.2% by mass.
The resin solution having a concentration of 20.2% by mass prepared above was placed in a 15 g, 250 ml disposable cup, and 1.22 g of MgF 2 powder (2) was added thereto as a filler. The concentration of filler, calculated the density of the resin 1.95 g / cm 3, the density of the MgF 2 powder as 3.15 g / cm 3, a 20% by volume. This solution is mixed with Awatori Rentaro ARV-310 at a rotation speed of 2000 rpm for 2 minutes three times to mix the solution and filler, and a magnetic stirrer is put therein and stirred to fill the filler. When 70 g of isopropyl alcohol (IPA, manufactured by Nacalai Tesque, Inc.) was added at once while maintaining the state in which the resin was uniformly fluttering in the solution, the resin gelled and precipitated at once while involving the filler and some solvent. did.
The gelled lumpy sample was taken out, the stirrer was taken out from the sample, and then placed on an aluminum cup and dried at room temperature. After drying for about 4 hours, it was cut into a size of about 3 cm square using scissors to accelerate the drying, and then dried overnight. The sample was cut into 5 mm square pieces with scissors and dried on a hot plate set at 100 ° C. for 3 hours.
Then, the sample was transferred to a petri dish made of PFA, defoamed and dried in a vacuum dryer at 200 ° C. for 3 hours. The sample was melted during drying and was agglomerated after drying. The obtained massive sample was cut again into a size of about 2 mm square using scissors to obtain pellets. The yield with respect to the total amount of the resin and the filler used was 100%.
A 0.1 mm thick, 15 cm square polytetrafluoroethylene (PTFE) film is laminated on a 5 mm thick, 15 cm square SUS plate, and a 3 cm square through hole is provided in the center on the PTFE film. A 0.5 mm, 15 cm square SUS plate was laminated. Next, 1.2 g of the pellet was placed in the through hole of the 3 cm square. Further, a 0.1 mm thick, 15 cm square PTFE film and a 5 mm thick, 15 cm square SUS plate were laminated in this order to assemble a mold. Next, the temperature of the press was set to 200 ° C., and the upper and lower plates of the press were held in contact with the SUS plates above and below the die for 3 minutes without pressurization to melt the pellets. Then, the pressure was increased at 50 MPa for 2 minutes. After pressurizing, the mold is taken out, and the mold is separately sandwiched between two SUS plates that have been passed through water and cooled sufficiently to disassemble the mold to obtain a fluororesin sheet containing a filler having a thickness of 0.5 mm. Obtained, the transmittance at 265 nm, 350 nm, and 500 nm was measured based on the following conditions. The results are shown in Table 4.
Measurement conditions Measuring device: Ultraviolet visible near infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation)
Attachment: Integrating sphere ISR-3100
Background measurement: Atmosphere
下記に記載の方法でシートを作製し、透過率を測定した。
実施例７
ウォーターバスに置いたセパラブルフラスコに、酢酸ブチル（富士フイルム和光純薬株式会社製）１６０ｇを測り入れ、攪拌しながら、ウォーターバスを８５℃まで昇温した。攪拌しながら、ＴＨＶ２２１ＡＺを少しずつ４０ｇ加えて溶解させ、樹脂溶液を作製した。得られた溶液を１２０℃、３時間加熱し、残分から固形分濃度を求めたところ２０．２質量％であった。
上記で作製した２０．２質量％の濃度の樹脂溶液を１５ｇ、２５０ｍｌのディスポカップに入れ、そこにフィラーとしてＭｇＦ2粉末（２）を１．２２ｇ添加した。フィラーの濃度は、樹脂の密度を１．９５ｇ／ｃｍ3、ＭｇＦ2粉末の密度を３．１５ｇ／ｃｍ3として計算すると、２０体積％である。この溶液を、あわとり練太郎ＡＲＶ－３１０を用いて、回転数２０００ｒｐｍで２分間混合する操作を３回実施して、溶液とフィラーとを混合し、そこにマグネットスターラーを入れて攪拌してフィラーが均一に溶液中に舞っている状態を維持しながら、イソプロピルアルコール（ＩＰＡ、ナカライテクス株式会社製）７０ｇを一気に入れたところ、フィラーと一部の溶媒を巻き込みながら、樹脂が一気にゲル化して析出した。
ゲル化した塊状の試料を取り出し、該試料からスターラーを取り出した後、アルミカップの上に置いて、常温で乾燥させた。４時間程度乾燥させたところで、乾燥を促進させるためにハサミを用いておおよそ３ｃｍ角ぐらいのサイズに切り、その後、一晩乾燥させた。試料をハサミで５ｍｍ角程度に切り、１００℃に設定したホットプレートの上で３時間乾燥させた。
その後、試料をＰＦＡ製のシャーレに移し、真空乾燥機中で２００℃で３時間、脱泡、および乾燥させた。乾燥中は、試料は溶融しており、乾燥後はひと塊になっていた。得られた塊状の試料を再度、ハサミを用いて、２ｍｍ角程度のサイズに切り、ペレットとした。使用した樹脂とフィラーの合計量に対する収率は１００％であった。
厚さ５ｍｍ、１５ｃｍ角のＳＵＳ板の上に厚さ０．１ｍｍ、１５ｃｍ角のポリテトラフルオロエチレン（ＰＴＦＥ）フィルムを積層し、ＰＴＦＥフィルムの上に、中心に３ｃｍ角の貫通孔を備える厚さ０．５ｍｍ、１５ｃｍ角のＳＵＳ板を積層した。次いで上記ペレットを、上記３ｃｍ角の貫通孔の中に１．２ｇ入れた。更に厚さ０．１ｍｍ、１５ｃｍ角のＰＴＦＥフィルムと、厚さ５ｍｍ、１５ｃｍ角のＳＵＳ板とを順に積層して金型を組立てた。次いで、プレス機の温度を２００℃に設定し、加圧せずにプレス機の上下板を金型の上下の上記ＳＵＳ板に接触させた状態で３分保持してペレットを溶融させた。その後５０ＭＰａの圧力で２分間加圧した。加圧後に金型を取り出して、別途、水を通した２枚のＳＵＳ板で金型を挟んで十分に冷却して、金型を分解して、０．５ｍｍ厚みのフィラー含有フッ素樹脂シートを得、２６５ｎｍ、３５０ｎｍ、及び５００ｎｍにおける透過率を下記の条件に基づいて測定した。結果を表４に示す。
測定条件
測定装置：紫外可視近赤外分光光度計ＵＶ－３６００（株式会社島津製作所製）
アタッチメント：積分球 ＩＳＲ－３１００
バックグラウンド測定：大気 <Transparency evaluation>
A sheet was prepared by the method described below, and the transmittance was measured.
Example 7
160 g of butyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was weighed into a separable flask placed in a water bath, and the temperature of the water bath was raised to 85 ° C. with stirring. While stirring, 40 g of THV221AZ was gradually added and dissolved to prepare a resin solution. The obtained solution was heated at 120 ° C. for 3 hours, and the solid content concentration was determined from the residue and found to be 20.2% by mass.
The resin solution having a concentration of 20.2% by mass prepared above was placed in a 15 g, 250 ml disposable cup, and 1.22 g of MgF 2 powder (2) was added thereto as a filler. The concentration of filler, calculated the density of the resin 1.95 g / cm 3, the density of the MgF 2 powder as 3.15 g / cm 3, a 20% by volume. This solution is mixed with Awatori Rentaro ARV-310 at a rotation speed of 2000 rpm for 2 minutes three times to mix the solution and filler, and a magnetic stirrer is put therein and stirred to fill the filler. When 70 g of isopropyl alcohol (IPA, manufactured by Nacalai Tesque, Inc.) was added at once while maintaining the state in which the resin was uniformly fluttering in the solution, the resin gelled and precipitated at once while involving the filler and some solvent. did.
The gelled lumpy sample was taken out, the stirrer was taken out from the sample, and then placed on an aluminum cup and dried at room temperature. After drying for about 4 hours, it was cut into a size of about 3 cm square using scissors to accelerate the drying, and then dried overnight. The sample was cut into 5 mm square pieces with scissors and dried on a hot plate set at 100 ° C. for 3 hours.
Then, the sample was transferred to a petri dish made of PFA, defoamed and dried in a vacuum dryer at 200 ° C. for 3 hours. The sample was melted during drying and was agglomerated after drying. The obtained massive sample was cut again into a size of about 2 mm square using scissors to obtain pellets. The yield with respect to the total amount of the resin and the filler used was 100%.
A 0.1 mm thick, 15 cm square polytetrafluoroethylene (PTFE) film is laminated on a 5 mm thick, 15 cm square SUS plate, and a 3 cm square through hole is provided in the center on the PTFE film. A 0.5 mm, 15 cm square SUS plate was laminated. Next, 1.2 g of the pellet was placed in the through hole of the 3 cm square. Further, a 0.1 mm thick, 15 cm square PTFE film and a 5 mm thick, 15 cm square SUS plate were laminated in this order to assemble a mold. Next, the temperature of the press was set to 200 ° C., and the upper and lower plates of the press were held in contact with the SUS plates above and below the die for 3 minutes without pressurization to melt the pellets. Then, the pressure was increased at 50 MPa for 2 minutes. After pressurizing, the mold is taken out, and the mold is separately sandwiched between two SUS plates that have been passed through water and cooled sufficiently to disassemble the mold to obtain a fluororesin sheet containing a filler having a thickness of 0.5 mm. Obtained, the transmittance at 265 nm, 350 nm, and 500 nm was measured based on the following conditions. The results are shown in Table 4.
Measurement conditions Measuring device: Ultraviolet visible near infrared spectrophotometer UV-3600 (manufactured by Shimadzu Corporation)
Attachment: Integrating sphere ISR-3100
Background measurement: Atmosphere
表３に示す通り、ＭｇＦ2粉末を含有しない比較例１では１０％質量変化温度が４００℃未満であり耐熱性に劣っていたが、ＭｇＦ2粉末を含有する実施例１～６では１０％質量変化温度が４００℃以上であり優れた耐熱性を発揮した。表２、３の結果より、樹脂組成物中に構成単位Ａのモル比（Ａ）が０．２５以上であり、且つ構成単位Ｃのモル比（Ｃ）が０．６０以下である本発明のフッ素樹脂と、無機フィラーとを含むことにより、優れた密着性と耐熱性を両立できることが分かる。
As shown in Table 3, in Comparative Example 1 not containing MgF 2 powder, the 10% mass change temperature was less than 400 ° C. and the heat resistance was inferior, but in Examples 1 to 6 containing MgF 2 powder, 10% mass was obtained. The change temperature was 400 ° C. or higher, and excellent heat resistance was exhibited. From the results of Tables 2 and 3, the molar ratio (A) of the constituent unit A in the resin composition is 0.25 or more, and the molar ratio (C) of the constituent unit C is 0.60 or less. It can be seen that by containing the fluororesin and the inorganic filler, both excellent adhesion and heat resistance can be achieved.
１ 紫外線発光装置
１ａ 紫外線発光装置
２ 紫外線発光素子
３ａ、３ｂ 樹脂組成物の固化物
４ 基材
５ バンプ
６ 紫外線発光素子実装パッケージ
７ 集光レンズ
１０ ｐ電極
１１ ｎ電極
１２ ｐ層
１３ 活性層
１４ ｎ層
１５ 基板 1 Ultraviolet light emitting device 1a Ultravioletlight emitting device 2 Ultraviolet light emitting element 3a, 3b Solidified resin composition 4 Base material 5 Bump 6 Ultraviolet light emitting element mounting package 7 Condensing lens 10 p electrode 11 n electrode 12 p layer 13 Active layer 14 n Layer 15 substrate
１ａ 紫外線発光装置
２ 紫外線発光素子
３ａ、３ｂ 樹脂組成物の固化物
４ 基材
５ バンプ
６ 紫外線発光素子実装パッケージ
７ 集光レンズ
１０ ｐ電極
１１ ｎ電極
１２ ｐ層
１３ 活性層
１４ ｎ層
１５ 基板 1 Ultraviolet light emitting device 1a Ultraviolet
Claims (12)
- フッ素樹脂、及び無機フィラーを含み、
前記フッ素樹脂は、テトラフルオロエチレン由来の構成単位Ａ、ヘキサフルオロプロピレン由来の構成単位Ｂ、及びフッ化ビニリデン由来の構成単位Ｃを含み、
前記構成単位Ａ、前記構成単位Ｂ、及び前記構成単位Ｃの合計に対する前記構成単位Ａのモル比（Ａ）が０．２５以上であり、
前記構成単位Ａ、前記構成単位Ｂ、及び前記構成単位Ｃの合計に対する前記構成単位Ｃのモル比（Ｃ）が０．６０以下であることを特徴とする樹脂組成物。 Contains fluororesin and inorganic filler
The fluororesin contains a constituent unit A derived from tetrafluoroethylene, a constituent unit B derived from hexafluoropropylene, and a constituent unit C derived from vinylidene fluoride.
The molar ratio (A) of the structural unit A to the total of the structural unit A, the structural unit B, and the structural unit C is 0.25 or more.
A resin composition, wherein the molar ratio (C) of the structural unit C to the total of the structural unit A, the structural unit B, and the structural unit C is 0.60 or less. - 前記構成単位Ａ、前記構成単位Ｂ、及び前記構成単位Ｃの合計に対する前記構成単位Ａのモル比（Ａ）が０．２５以上、０．７５以下である請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the molar ratio (A) of the structural unit A to the total of the structural unit A, the structural unit B, and the structural unit C is 0.25 or more and 0.75 or less.
- 前記構成単位Ａ、前記構成単位Ｂ、及び前記構成単位Ｃの合計に対する前記構成単位Ｃのモル比（Ｃ）が０．２０以上、０．６０以下である請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the molar ratio (C) of the structural unit C to the total of the structural unit A, the structural unit B, and the structural unit C is 0.20 or more and 0.60 or less. Stuff.
- 前記構成単位Ａ、前記構成単位Ｂ、及び前記構成単位Ｃの合計に対する前記構成単位Ｂのモル比（Ｂ）が０．０５以上、０．５０以下である請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the molar ratio (B) of the structural unit B to the total of the structural unit A, the structural unit B, and the structural unit C is 0.05 or more and 0.50 or less.
- 前記モル比（Ｃ）の前記モル比（Ａ）に対する比（モル比（Ｃ）／モル比（Ａ））が０．２０以上、３．５０以下である請求項３に記載の樹脂組成物。 The resin composition according to claim 3, wherein the ratio of the molar ratio (C) to the molar ratio (A) (molar ratio (C) / molar ratio (A)) is 0.20 or more and 3.50 or less.
- 前記モル比（Ｂ）の前記モル比（Ａ）に対する比（モル比（Ｂ）／モル比（Ａ））が、０．１０以上、０．８０以下である請求項４に記載の樹脂組成物。 The resin composition according to claim 4, wherein the ratio of the molar ratio (B) to the molar ratio (A) (molar ratio (B) / molar ratio (A)) is 0.10 or more and 0.80 or less. ..
- 前記無機フィラーが金属フッ化物である請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the inorganic filler is a metal fluoride.
- 前記無機フィラーの粒径が３００μｍ以下である請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the inorganic filler has a particle size of 300 μm or less.
- 前記フッ素樹脂、及び前記無機フィラーの合計１００質量部に対する前記無機フィラーの量が１質量部以上、６０質量部以下である請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the amount of the inorganic filler is 1 part by mass or more and 60 parts by mass or less with respect to a total of 100 parts by mass of the fluororesin and the inorganic filler.
- 前記フッ素樹脂と前記無機フィラーとの屈折率の差が０．０５以下である請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the difference in refractive index between the fluororesin and the inorganic filler is 0.05 or less.
- 紫外線発光素子の封止に用いられるものである請求項１に記載の樹脂組成物。 The resin composition according to claim 1, which is used for sealing an ultraviolet light emitting element.
- 紫外線発光素子を備え、
前記紫外線発光素子が、請求項１に記載の樹脂組成物の固化物により封止されていることを特徴とする紫外線発光装置。 Equipped with an ultraviolet light emitting element
An ultraviolet light emitting device, wherein the ultraviolet light emitting element is sealed with a solidified product of the resin composition according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019092838 | 2019-05-16 | ||
| JP2019-092838 | 2019-05-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2020230714A1 true WO2020230714A1 (en) | 2020-11-19 |
Family
ID=73290083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2020/018653 WO2020230714A1 (en) | 2019-05-16 | 2020-05-08 | Resin composition and ultraviolet light-emitting device |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2020189964A (en) |
| TW (1) | TW202043362A (en) |
| WO (1) | WO2020230714A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021153336A1 (en) * | 2020-01-30 | 2021-08-05 | 住友化学株式会社 | Fluororesin sheet and method for producing same |
| WO2021153335A1 (en) * | 2020-01-30 | 2021-08-05 | 住友化学株式会社 | Electronic component and method for manufacturing same |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004039883A1 (en) * | 2002-10-29 | 2004-05-13 | Daikin Industries, Ltd. | Fluororesin composition, molded fluororesin articles, fluororesin laminates and use of the laminates |
| JP2013175462A (en) * | 2012-02-24 | 2013-09-05 | Daikin Ind Ltd | Electric wire coating material and electric wire |
| JP2014185294A (en) * | 2013-03-25 | 2014-10-02 | Mitsubishi Chemicals Corp | Resin composition, reflection member, light-emitting device and lighting apparatus |
| WO2014178288A1 (en) * | 2013-04-30 | 2014-11-06 | 創光科学株式会社 | Ultraviolet light-emitting device |
| US20170229614A1 (en) * | 2014-07-30 | 2017-08-10 | Lg Innotek Co., Ltd. | Light emitting device and light source module having thereof |
| JP2017149839A (en) * | 2016-02-24 | 2017-08-31 | ダイキン工業株式会社 | Fluorine rubber composition and molding |
| US20170263833A1 (en) * | 2016-03-14 | 2017-09-14 | Lite-On Opto Technology (Changzhou) Co., Ltd. | Led package structure |
| JP2017532426A (en) * | 2014-10-31 | 2017-11-02 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Fluoroelastomer composition |
-
2020
- 2020-03-31 JP JP2020064770A patent/JP2020189964A/en active Pending
- 2020-05-08 WO PCT/JP2020/018653 patent/WO2020230714A1/en active Application Filing
- 2020-05-11 TW TW109115495A patent/TW202043362A/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004039883A1 (en) * | 2002-10-29 | 2004-05-13 | Daikin Industries, Ltd. | Fluororesin composition, molded fluororesin articles, fluororesin laminates and use of the laminates |
| JP2013175462A (en) * | 2012-02-24 | 2013-09-05 | Daikin Ind Ltd | Electric wire coating material and electric wire |
| JP2014185294A (en) * | 2013-03-25 | 2014-10-02 | Mitsubishi Chemicals Corp | Resin composition, reflection member, light-emitting device and lighting apparatus |
| WO2014178288A1 (en) * | 2013-04-30 | 2014-11-06 | 創光科学株式会社 | Ultraviolet light-emitting device |
| US20170229614A1 (en) * | 2014-07-30 | 2017-08-10 | Lg Innotek Co., Ltd. | Light emitting device and light source module having thereof |
| JP2017532426A (en) * | 2014-10-31 | 2017-11-02 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Fluoroelastomer composition |
| JP2017149839A (en) * | 2016-02-24 | 2017-08-31 | ダイキン工業株式会社 | Fluorine rubber composition and molding |
| US20170263833A1 (en) * | 2016-03-14 | 2017-09-14 | Lite-On Opto Technology (Changzhou) Co., Ltd. | Led package structure |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021153336A1 (en) * | 2020-01-30 | 2021-08-05 | 住友化学株式会社 | Fluororesin sheet and method for producing same |
| WO2021153335A1 (en) * | 2020-01-30 | 2021-08-05 | 住友化学株式会社 | Electronic component and method for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202043362A (en) | 2020-12-01 |
| JP2020189964A (en) | 2020-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020230714A1 (en) | Resin composition and ultraviolet light-emitting device | |
| WO2020230716A1 (en) | Electronic component production method and electronic component | |
| JP5783902B2 (en) | Opaque fluoropolymer compositions containing white pigments for photovoltaic elements of solar cells | |
| TWI360583B (en) | ||
| TWI629305B (en) | Composition for interlayer filler of laminated semiconductor device, laminated semiconductor device, and method for manufacturing laminated semiconductor device | |
| WO2011065016A1 (en) | Substrate for led mounting | |
| TWI600777B (en) | Sputtering target and its manufacturing method | |
| TWI592950B (en) | Paste for solar cell electrode and solar cell electrode prepared using the same | |
| JPWO2020153505A1 (en) | Filler composition, silicone resin composition and heat dissipation parts | |
| TWI461438B (en) | Film based on fluoropolymer and on zinc oxide without acrylic odour for photovoltaic application | |
| JP2023017869A (en) | Sintered metal powder paste, method for producing the same, and method for producing conductive material | |
| CN113853690A (en) | Electronic component and method for manufacturing the same | |
| JP2021109825A (en) | Heat-conductive filler and heat-conductive composition containing the same | |
| JP2021161270A (en) | Resin molding, ultraviolet light-emitting device, and method for manufacturing resin molding | |
| JP6365922B2 (en) | Sputtering target and manufacturing method thereof | |
| CN109233577A (en) | Nonaqueous electrolytic solution secondary battery coating | |
| JP2021163876A (en) | Electronic device | |
| JP2016124908A (en) | Resin molded body | |
| WO2021153337A1 (en) | Fluororesin and method for producing same | |
| JP2021161271A (en) | Fluororesin sheet and electronic apparatus | |
| JP2023124592A (en) | Resin composition and NaMgF3 filler | |
| TW201432066A (en) | Sputtering target and producing method thereof | |
| KR20190016856A (en) | Thermoconductive high internal phase emulsion and heat dissipative composite using the same | |
| JP6998362B2 (en) | Electronic components and their manufacturing methods | |
| WO2021200279A1 (en) | Fluororesin sheet and method for producing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20806700 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 20806700 Country of ref document: EP Kind code of ref document: A1 |